U.S. patent application number 17/131891 was filed with the patent office on 2021-07-01 for multilayer ceramic capacitor.
The applicant listed for this patent is Murata Manufacturing Co., Ltd.. Invention is credited to Daiki FUKUNAGA, Yuta KUROSU, Yuta SAITO, Yu TSUTSUI, Masahiro WAKASHIMA.
Application Number | 20210202178 17/131891 |
Document ID | / |
Family ID | 1000005372724 |
Filed Date | 2021-07-01 |
United States Patent
Application |
20210202178 |
Kind Code |
A1 |
KUROSU; Yuta ; et
al. |
July 1, 2021 |
MULTILAYER CERAMIC CAPACITOR
Abstract
In a multilayer ceramic capacitor, an intersection of an
interface is defined by a second dielectric ceramic layer, a first
internal electrode layer or a second internal electrode layer, and
a third dielectric ceramic layer, on a plane including a length
direction and a width direction, the second dielectric ceramic
layer and the third dielectric ceramic layer include a near
intersection region at or near the intersection, and an average
particle size of dielectric particles in the near intersection
region is smaller than average particle sizes of dielectric
particles in the first dielectric ceramic layer, the second
dielectric ceramic layer, and the third dielectric ceramic
layer.
Inventors: |
KUROSU; Yuta;
(Nagaokakyo-shi, JP) ; SAITO; Yuta;
(Nagaokakyo-shi, JP) ; WAKASHIMA; Masahiro;
(Nagaokakyo-shi, JP) ; FUKUNAGA; Daiki;
(Nagaokakyo-shi, JP) ; TSUTSUI; Yu;
(Nagaokakyo-shi, JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Murata Manufacturing Co., Ltd. |
Nagaokakyo-shi |
|
JP |
|
|
Family ID: |
1000005372724 |
Appl. No.: |
17/131891 |
Filed: |
December 23, 2020 |
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
H01G 4/008 20130101;
H01G 4/30 20130101; H01G 4/1227 20130101; H01G 4/012 20130101; C04B
35/4682 20130101; C04B 2235/401 20130101 |
International
Class: |
H01G 4/30 20060101
H01G004/30; H01G 4/012 20060101 H01G004/012; H01G 4/12 20060101
H01G004/12; H01G 4/008 20060101 H01G004/008; C04B 35/468 20060101
C04B035/468 |
Foreign Application Data
Date |
Code |
Application Number |
Dec 27, 2019 |
JP |
2019-238184 |
Nov 6, 2020 |
JP |
2020-186018 |
Claims
1. A multilayer ceramic capacitor comprising: a multilayer body
including a dielectric ceramic layer and an internal electrode
layer stacked in a stacking direction; and an external electrode
connected to the internal electrode layer; wherein the multilayer
body includes a first main surface and a second main surface on
opposite sides in the stacking direction, a first side surface and
a second side surface on opposite sides in a width direction
orthogonal or substantially orthogonal to the stacking direction,
and a first end surface and a second end surface on opposite sides
in a length direction orthogonal or substantially orthogonal to the
stacking direction and the width direction; the internal electrode
layer includes a first internal electrode layer that extends to the
first end surface, and a second internal electrode layer that
extends to the second end surface opposite to the first internal
electrode layer with the dielectric ceramic layer interposed
therebetween; the external electrode includes a first external
electrode that is disposed on the first end surface and is
connected to the first internal electrode layer, and a second
external electrode that is disposed on the second end surface and
is connected to the second internal electrode layer; the dielectric
ceramic layer includes a first dielectric ceramic layer and a
second dielectric ceramic layer; the first dielectric ceramic layer
is disposed between the first internal electrode layer and the
second internal electrode layer; the second dielectric ceramic
layer includes a region between the first dielectric ceramic layers
opposite to each other with the internal electrode layer interposed
therebetween, and in which the internal electrode layer is not
disposed, and so that a portion of the second dielectric ceramic
layer overlaps the first dielectric ceramic layer in the stacking
direction; the multilayer body includes an inner layer portion in
which the first internal electrode layer and the second internal
electrode layer are alternately stacked with the dielectric ceramic
layer interposed therebetween, an outer layer portion that
sandwiches the inner layer portion in the stacking direction and
includes a ceramic material, and a third dielectric ceramic layer
that sandwiches the inner layer portion and the outer layer portion
in the width direction and includes a dielectric ceramic material;
an intersection of an interface is defined by the second dielectric
ceramic layer, the first internal electrode layer or the second
internal electrode layer, and the third dielectric ceramic layer,
on a plane including the length direction and the width direction;
the second dielectric ceramic layer and the third dielectric
ceramic layer include a near intersection region in a vicinity of
the intersection of the interface; and an average particle size of
dielectric particles included in the near intersection region is
smaller than an average particle size of dielectric particles
included in the first dielectric ceramic layer, an average particle
size of dielectric particles included in the second dielectric
ceramic layer, and an average particle size of dielectric particles
included in the third dielectric ceramic layer.
2. The multilayer ceramic capacitor according to claim 1, wherein
the average particle size of dielectric particles included in the
near intersection region is about 5% or more smaller than the
average particle size of dielectric particles included in the first
dielectric ceramic layer, the average particle size of dielectric
particles included in the second dielectric ceramic layer, and the
average particle size of dielectric particles included in the third
dielectric ceramic layer.
3. The multilayer ceramic capacitor according to claim 1, wherein a
difference between the average particle size of dielectric
particles included in the second dielectric ceramic layer and the
average particle size of dielectric particles included in the third
dielectric ceramic layer is within about 5%; the average particle
size of dielectric particles included in the first dielectric
ceramic layer is larger than the average particle size of
dielectric particles included in the second dielectric ceramic
layer and the average particle size of dielectric particles
included in the third dielectric ceramic layer; and the average
particle size of dielectric particles included in the near
intersection region is smaller than the average particle size of
dielectric particles included in the second dielectric ceramic
layer and the average particle size of dielectric particles
included in the third dielectric ceramic layer.
4. The multilayer ceramic capacitor according to claim 1, wherein a
difference between the average particle size of dielectric
particles included in the first dielectric ceramic layer and the
average particle size of dielectric particles included in the
second dielectric ceramic layer is within about 5%; the average
particle size of dielectric particles included in the third
dielectric ceramic layer is smaller than the average particle size
of dielectric particles included in the first dielectric ceramic
layer and the average particle size of dielectric particles
included in the second dielectric ceramic layer; and the average
particle size of dielectric particles included in the near
intersection region is smaller than the average particle size of
dielectric particles included in the third dielectric ceramic
layer.
5. The multilayer ceramic capacitor according to claim 1, wherein a
difference between the average particle size of dielectric
particles included in the first dielectric ceramic layer and the
average particle size of dielectric particles included in the third
dielectric ceramic layer is within about 5%; the average particle
size of dielectric particles included in the second dielectric
ceramic layer is smaller than the average particle size of
dielectric particles included in the first dielectric ceramic layer
and the average particle size of dielectric particles included in
the third dielectric ceramic layer; and the average particle size
of dielectric particles included in the near intersection region is
smaller than the average particle size of dielectric particles
included in the second dielectric ceramic layer.
6. The multilayer ceramic capacitor according to claim 1, wherein a
difference between the average particle size of dielectric
particles included in the first dielectric ceramic layer and the
average particle size of dielectric particles included in the
second dielectric ceramic layer, the difference between the average
particle size of dielectric particles included in the first
dielectric ceramic layer and the average particle size of
dielectric particles included in the third dielectric ceramic
layer, and a difference between the average particle size of
dielectric particles included in the second dielectric ceramic
layer and the average particle size of dielectric particles
included in the third dielectric ceramic layer are all within about
5%; the average particle size of dielectric particles included in
the near intersection region is smaller than the average particle
size of dielectric particles included in the first dielectric
ceramic layer, the average particle size of dielectric particles
included in the second dielectric ceramic layer, and the average
particle size of dielectric particles included in the third
dielectric ceramic layer.
7. The multilayer ceramic capacitor according to claim 1, wherein
the average particle size of dielectric particles included in the
first dielectric ceramic layer is smaller than the average particle
size of dielectric particles included in the second dielectric
ceramic layer; the average particle size of dielectric particles
included in the third dielectric ceramic layer is smaller than the
average particle size of dielectric particles included in the first
dielectric ceramic layer; and the average particle size of
dielectric particles included in the near intersection region is
smaller than the average particle size of dielectric particles
included in the third dielectric ceramic layer.
8. The multilayer ceramic capacitor according to claim 1, wherein
the average particle size of dielectric particles included in the
first dielectric ceramic layer is smaller than the average particle
size of dielectric particles included in the third dielectric
ceramic layer; the average particle size of dielectric particles
included in the second dielectric ceramic layer is smaller than the
average particle size of dielectric particles included in the first
dielectric ceramic layer; and the average particle size of
dielectric particles included in the near intersection region is
smaller than the average particle size of dielectric particles
included in the second dielectric ceramic layer.
9. The multilayer ceramic capacitor according to claim 1, wherein
the average particle size of dielectric particles included in the
near intersection region is smaller than the average particle size
of dielectric particles included in the first dielectric ceramic
layer; and the average particle size of dielectric particles
included in the third dielectric ceramic layer or the average
particle size of dielectric particles included in the second
dielectric ceramic layer is smaller than the average particle size
of dielectric particles included in the near intersection
region.
10. The multilayer ceramic capacitor according to claim 1, wherein
each of the first external electrode and the second external
electrode includes a metal and a ceramic material.
11. The multilayer ceramic capacitor according to claim 1, wherein
each of the first external electrode and the second external
electrode includes a Ni layer, a first plated layer, and a second
plated layer.
12. The multilayer ceramic capacitor according to claim 11, wherein
each of the first external electrode and the second external
electrode further includes a Cu layer.
13. The multilayer ceramic capacitor according to claim 1, wherein
the outer layer portion includes a plurality of dielectric ceramic
layers.
14. The multilayer ceramic capacitor according to claim 1, wherein
the dielectric ceramic layer includes ceramic grains.
15. The multilayer ceramic capacitor according to claim 1, wherein
a thickness of the outer layer portion is about 15 .mu.m or more
and about 40 .mu.m or less.
16. The multilayer ceramic capacitor according to claim 1, wherein
the first dielectric ceramic layer includes Mg; the second
dielectric ceramic layer includes Sn; and the third dielectric
ceramic layer includes at least one metal element selected from a
group consisting of Mg, Mn, and Si.
17. The multilayer ceramic capacitor according to claim 1, wherein
the dielectric ceramic layer includes a rare earth element in an
amount of about 0.2 mol % or more and about 5 mol % or less with
respect to 100 moles of Ti.
18. The multilayer ceramic capacitor according to claim 1, wherein
the dielectric ceramic layer has a perovskite structure as a main
component.
19. The multilayer ceramic capacitor according to claim 1, wherein
a thickness of each of the first internal electrode layer and the
second internal electrode layer is about 0.25 .mu.m or more and
about 0.4 .mu.m or less.
20. The multilayer ceramic capacitor according to claim 1, wherein
a thickness of each of the first dielectric ceramic layer and the
second dielectric ceramic layer is about 0.4 .mu.m or more and
about 0.55 .mu.m or less.
Description
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application claims the benefit of priority to Japanese
Patent Application No. 2019-238184 filed on Dec. 27, 2019 and
Japanese Patent Application No. 2020-186018 filed on Nov. 6, 2020.
The entire contents of these applications are hereby incorporated
herein by reference.
BACKGROUND OF THE INVENTION
1. Field of the Invention
[0002] The present invention relates to a multilayer ceramic
capacitor.
2. Description of the Related Art
[0003] In recent years, multilayer ceramic electronic components
such as multilayer ceramic capacitors have been miniaturized and
developed to generate higher capacitance. To achieve
miniaturization and higher capacitance of the multilayer ceramic
capacitors, it is advantageous to reduce the thickness of the side
margin with respect to each side surface of a multilayer body in
which a plurality of dielectric ceramic layers and a plurality of
internal electrode layers are stacked, to thus increase the area of
the internal electrode layers provided opposite to each other.
[0004] Japanese Unexamined Patent Application Publication No.
2017-147358 discloses a method for manufacturing an electronic
component including a step of preparing a chip in which a plurality
of dielectric ceramic layers and a plurality of internal electrode
layers are stacked, the plurality of internal electrode layers
being exposed on a side surface, a step of pasting a plurality of
covering dielectric sheets to each other to form a dielectric
laminated sheet, and a step of applying the dielectric laminated
sheet on a side surface of the chip.
[0005] Furthermore, Japanese Unexamined Patent Application
Publication No. 2003-209025 discloses that, by applying a ceramic
slurry for level difference elimination in an area in which
internal electrodes are not printed, upon producing a multilayer
ceramic capacitor by stacking a plurality of ceramic green sheets
each having internal electrodes printed therein, and then
pressurizing and firing, it is possible to prevent the level
difference generated between a portion in which the internal
electrodes overlap with each other and a portion in which the
internal electrodes do not overlap with each other.
[0006] However, Japanese Unexamined Patent Application Publication
No. 2017-147358 does not specifically describe the composition of a
ceramic dielectric sheet to be bonded to the side surface of the
multilayer body. Japanese Unexamined Patent Application Publication
No. 2003-209025 does not specifically describe the composition of a
ceramic paste for level difference elimination used in Japanese
Unexamined Patent Application Publication No. 2003-209025.
Therefore, in Japanese Unexamined Patent Application Publication
No. 2017-147358 and Japanese Unexamined Patent Application
Publication No. 2003-209025, there is room to improve the
reliability of multilayer ceramic capacitors by optimizing the
composition of the dielectric laminated sheet and the composition
of the ceramic paste for level difference elimination. Furthermore,
since the electric field is concentrated at the ends of the
internal electrodes in close proximity to the ceramic paste for
level difference elimination disclosed in Japanese Unexamined
Patent Application Publication No. 2003-209025, the reliability may
be degraded.
SUMMARY OF THE INVENTION
[0007] Preferred embodiments of the present invention provide
multilayer ceramic capacitors each capable of reducing or
preventing electric field concentration at least at an end of an
internal electrode thus improving reliability.
[0008] A multilayer ceramic capacitor according to a preferred
embodiment of the present invention includes a multilayer body
including a dielectric ceramic layer and an internal electrode
layer stacked in a stacking direction; and an external electrode
connected to the internal electrode layer, wherein the multilayer
body includes a first main surface and a second main surface on
opposite sides in the stacking direction, a first side surface and
a second side surface on opposite sides in a width direction
orthogonal or substantially orthogonal to the stacking direction,
and a first end surface and a second end surface on opposite sides
in a length direction orthogonal or substantially orthogonal to the
stacking direction and the width direction, the internal electrode
layer includes a first internal electrode layer that extends to the
first end surface, and a second internal electrode layer that
extends to the second end surface opposite to the first internal
electrode layer with the dielectric ceramic layer interposed
therebetween, the external electrode includes a first external
electrode that is disposed on the first end surface and is
connected to the first internal electrode layer, and a second
external electrode that is disposed on the second end surface and
is connected to the second internal electrode layer, the dielectric
ceramic layer includes a first dielectric ceramic layer and a
second dielectric ceramic layer, the first dielectric ceramic layer
is between the first internal electrode layer and the second
internal electrode layer, the second dielectric ceramic layer
includes a region between the first dielectric ceramic layers
opposite to each other with the internal electrode layer interposed
therebetween, and in which the internal electrode layer is not
provided, and so that a portion of the second dielectric ceramic
layer overlaps the first dielectric ceramic layer in the stacking
direction, the multilayer body includes an inner layer portion in
which the first internal electrode layer and the second internal
electrode layer are alternately stacked with the dielectric ceramic
layer interposed therebetween, an outer layer portion that
sandwiches the inner layer portion in the stacking direction and
includes a ceramic material, and a third dielectric ceramic layer
that sandwiches the inner layer portion and the outer layer portion
in the width direction and includes a dielectric ceramic material,
an intersection of an interface is defined by the second dielectric
ceramic layer, the first internal electrode layer or the second
internal electrode layer, and the third dielectric ceramic layer,
on a plane including the length direction and the width direction,
the second dielectric ceramic layer and the third dielectric
ceramic layer include a near intersection region in a vicinity of
the intersection, and an average particle size of dielectric
particles in the near intersection region is smaller than an
average particle size of dielectric particles in the first
dielectric ceramic layer, an average particle size of dielectric
particles in the second dielectric ceramic layer, and an average
particle size of dielectric particles in the third dielectric
ceramic layer.
[0009] According to preferred embodiments of the present invention,
it is possible to provide multilayer ceramic capacitors each
capable of reducing or preventing electric field concentration at
least at the end of the internal electrode to improve
reliability.
[0010] The above and other elements, features, steps,
characteristics and advantages of the present invention will become
more apparent from the following detailed description of the
preferred embodiments with reference to the attached drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0011] FIG. 1 is a perspective view schematically showing an
example of a multilayer ceramic capacitor according to a preferred
embodiment of the present invention.
[0012] FIG. 2 is a perspective view schematically showing an
example of a multilayer body included in the multilayer ceramic
capacitor shown in FIG. 1.
[0013] FIG. 3 is a sectional view taken along line A-A of the
multilayer ceramic capacitor shown in FIG. 1.
[0014] FIG. 4 is a sectional view taken along line C-C of the
multilayer ceramic capacitor shown in FIG. 1.
[0015] FIG. 5 is a sectional view taken along line B-B of the
multilayer ceramic capacitor shown in FIG. 1.
[0016] FIG. 6 is a plan view schematically showing an example of a
ceramic green sheet.
[0017] FIG. 7 is a plan view schematically showing an example of a
ceramic green sheet.
[0018] FIG. 8 is a plan view schematically showing an example of a
ceramic green sheet.
[0019] FIG. 9 is an exploded perspective view schematically showing
an example of a mother block.
[0020] FIG. 10 is a perspective view schematically showing an
example of a green chip.
[0021] FIG. 11 shows a portion of an LT cross-section of a
multilayer ceramic capacitor according to a preferred embodiment of
the present invention, and is a diagram schematically showing a
first alloy portion and a second alloy portion.
[0022] FIG. 12 is a partially enlarged view of FIG. 11.
[0023] FIG. 13 shows a portion of an LT cross-section of a
multilayer ceramic capacitor according to a preferred embodiment of
the present invention, and is a diagram schematically showing a
first interspersed internal electrode, a second interspersed
internal electrode, and a fourth alloy portion.
[0024] FIG. 14 shows a portion of a WT cross-section of a
multilayer ceramic capacitor according to a preferred embodiment of
the present invention, and is a diagram schematically showing a
first alloy portion and a third alloy portion.
[0025] FIG. 15 is a partially enlarged view of FIG. 14, and
schematically shows a fifth alloy portion.
[0026] FIG. 16 shows a cross-sectional view schematically showing a
mode in which an end of a second dielectric ceramic layer is
superimposed on an end of an internal electrode layer in a
multilayer ceramic capacitor according to a preferred embodiment of
the present invention.
[0027] FIG. 17 shows a cross-sectional view schematically showing a
mode in which the end of the second dielectric ceramic layer is
superimposed on the end of the internal electrode layer in a
multilayer ceramic capacitor according to a preferred embodiment of
the present invention.
[0028] FIG. 18 is a diagram for explaining a TEM analysis method
for analyzing the amount of a metal element included in the
internal electrode layer of a multilayer ceramic capacitor
according to a preferred embodiment of the present invention.
[0029] FIG. 19 is a partial view of FIG. 5, and shows a near
intersection region according to a preferred embodiment of the
present invention.
[0030] FIG. 20 is a diagram for explaining a method for measuring
the average particle size of dielectric particles included in a
first dielectric ceramic layer and a third dielectric ceramic
layer.
[0031] FIG. 21 is a diagram for explaining a method for measuring
the average particle size of the dielectric particles included in
the third dielectric ceramic layer.
[0032] FIG. 22 is a diagram for explaining a first stage of a
method for measuring the average particle size of the dielectric
particles included in the second dielectric ceramic layer and the
near intersection region.
[0033] FIG. 23 is a diagram for explaining a second stage of a
method for measuring the average particle size of the dielectric
particles included in the second dielectric ceramic layer and the
near intersection region.
[0034] FIG. 24 is a diagram for explaining a method for measuring
the average particle size of the dielectric particles included in
the near intersection region.
[0035] FIG. 25 is a diagram schematically showing a step of
removing a side surface of an unfired multilayer body in a method
for manufacturing a multilayer ceramic capacitor according to a
preferred embodiment of the present invention.
[0036] FIG. 26 is a diagram showing an end surface of an unfired
multilayer body in which a side surface is removed in a method for
manufacturing a multilayer ceramic capacitor according to a
preferred embodiment of the present invention.
[0037] FIG. 27 is a cross-sectional view schematically showing a
mode in which an end of the second dielectric ceramic layer is
superimposed on an end of the internal electrode layer in a method
for manufacturing a multilayer ceramic capacitor according to a
preferred embodiment of the present invention.
[0038] FIG. 28 shows a portion of a WT cross-section of a
multilayer ceramic capacitor according to a preferred embodiment of
the present invention, and is a diagram schematically showing a
defect portion of the second dielectric ceramic layer.
[0039] FIG. 29 is a cross-sectional view taken along line K-K in
FIG. 28.
[0040] FIG. 30 shows a portion of a LT cross-section of a
multilayer ceramic capacitor according to a preferred embodiment of
the present invention, and is a diagram schematically showing a
first segregation.
[0041] FIG. 31 is a partially enlarged view of FIG. 30.
[0042] FIG. 32 shows a portion of a WT cross-section of a
multilayer ceramic capacitor according to a preferred embodiment of
the present invention, and is a diagram schematically showing a
second segregation.
[0043] FIG. 33 shows a portion of a LW cross-section of a
multilayer ceramic capacitor according to a preferred embodiment of
the present invention, and is a diagram showing a third segregation
which segregates in a first corner region and a second corner
region.
[0044] FIG. 34 is a cross-sectional view schematically showing a
mode in which an end of the second dielectric ceramic layer is
superimposed on the third segregation in a multilayer ceramic
capacitor according to a preferred embodiment of the present
invention.
[0045] FIG. 35 is a diagram showing the thickness of the first
dielectric ceramic layer at the central portion in the length (L)
direction of a multilayer ceramic capacitor according to a
preferred embodiment of the present invention.
[0046] FIG. 36 is a diagram showing the thickness of the second
dielectric ceramic layer of a multilayer ceramic capacitor
according to a preferred embodiment of the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0047] Hereinafter, multilayer ceramic capacitors according to
preferred embodiments of the present invention will be described
with reference to the drawings. However, the present invention is
not limited to the following preferred embodiments, and can be
applied by modifying where appropriate within a scope not changing
the gist of the present invention. It should be noted that
preferred embodiments of the present invention also includes
combinations of two or more of the individual preferred embodiments
described below.
Multilayer Ceramic Capacitor
[0048] FIG. 1 is a perspective view schematically showing an
example of a multilayer ceramic capacitor according to a preferred
embodiment of the present invention. FIG. 2 is a perspective view
schematically showing an example of a multilayer body (for example,
a laminate) included in the multilayer ceramic capacitor shown in
FIG. 1. FIG. 3 is a cross-sectional view taken along line A-A of
the multilayer ceramic capacitor shown in FIG. 1. FIG. 4 is a
cross-sectional view taken along line C-C of the multilayer ceramic
capacitor shown in FIG. 1.
[0049] In the present disclosure, a stacking direction (for
example, lamination direction), a width direction, and a length
direction of the multilayer ceramic capacitor and the multilayer
body are respectively defined by the arrows T, W, and L in the
multilayer ceramic capacitor 1 shown in FIG. 1 and the multilayer
body 10 shown in FIG. 2. Herein, the stacking (T) direction, the
width (W) direction, and the length (L) direction are orthogonal or
substantially orthogonal to one another. The stacking (T) direction
refers to a direction in which a plurality of dielectric ceramic
layers 20, and a plurality of pairs of a first internal electrode
layer 21 and a second internal electrode layer 22 are stacked.
[0050] The multilayer ceramic capacitor 1 shown in FIG. 1 includes
the multilayer body 10, and a first external electrode 51 and a
second external electrode 52 provided on both end surfaces of the
multilayer body 10, respectively.
[0051] As shown in FIG. 2, the multilayer body 10 has a rectangular
shape or a substantially rectangular shape. The multilayer body 10
includes a first main surface 11 and a second main surface 12 on
opposite sides in the stacking (T) direction, a first side surface
13 and a second side surface 14 on opposite sides in the width (W)
direction which is orthogonal or substantially orthogonal to the
stacking (T) direction, and a first end surface 15 and a second end
surface 16 on opposite sides in the length (L) direction which is
orthogonal or substantially orthogonal to the stacking (T)
direction and the width (W) direction.
[0052] In the present disclosure, a cross-section of the multilayer
ceramic capacitor 1 or the multiplayer body 10 which is orthogonal
or substantially orthogonal to the first end surface 15 and the
second end surface 16, and parallel or substantially parallel to
the stacking (T) direction refers to the LT cross-section, which is
a cross-section in the length (L) direction and the stacking (T)
direction. Furthermore, a cross-section of the multilayer ceramic
capacitor 1 or the multiplayer body 10 which is orthogonal or
substantially orthogonal to the first side surface 13 and the
second side surface 14, and parallel or substantially parallel to
the stacking (T) direction refers to WT cross-section, which is a
cross-section in the width (W) direction and the stacking (T)
direction. Furthermore, a cross-section of the multilayer ceramic
capacitor 1 or the multiplayer body 10 which is orthogonal or
substantially orthogonal to the first side surface 13, the second
side surface 14, the first end surface 15, and the second end
surface 16, and orthogonal or substantially orthogonal to the
stacking (T) direction refers to LW cross-section, which is a
cross-section in the length (L) direction and the width (W)
direction. Therefore, FIG. 3 is an LT cross-section of the
multilayer ceramic capacitor 1, and FIG. 4 is a WT cross-section of
the multilayer ceramic capacitor 1.
[0053] The multilayer body 10 preferably has rounded corners and
ridges. The corners are portions where the three surfaces of the
multilayer body intersect, and the ridges are portions where the
two surfaces of the multilayer body intersect.
[0054] As shown in FIGS. 2, 3 and 4, the multilayer body 10 has a
multilayer structure including a plurality of dielectric ceramic
layers 20 stacked in the stacking (T) direction, and a plurality of
pairs of the first internal electrode layer 21 and the second
internal electrode layer 22 provided along the interface between
the dielectric ceramic layers 20. The dielectric ceramic layer 20
extends along the width (W) direction and the length (L) direction,
and each of the first internal electrode layer 21 and the second
internal electrode layer 22 extends in a flat plate shape along the
dielectric ceramic layer 20.
[0055] The first internal electrode layer 21 extends to the first
end surface 15 of the multilayer body 10. On the other hand, the
second internal electrode layer 22 extends to the second end
surface 16 of the multilayer body 10.
[0056] The first internal electrode layer 21 and the second
internal electrode layer 22 are provided opposite to each other
with the dielectric ceramic layer 20 interposed therebetween in the
stacking (T) direction. Capacitance is generated by a portion where
the first internal electrode layer 21 and the second internal
electrode layer 22 are provided opposite to each other with the
dielectric ceramic layer 20 interposed therebetween.
[0057] Each of the first internal electrode layer 21 and the second
internal electrode layer 22 preferably includes a metal such as Ni,
Cu, Ag, Pd, or Au, or Ag--Pd alloy, for example. Each of the first
internal electrode layer 21 and the second internal electrode layer
22 may include the same dielectric ceramic material as that of the
dielectric ceramic layer 20, in addition to the metal.
[0058] The dielectric ceramic layer 20 includes a first dielectric
ceramic layer 20a, and a second dielectric ceramic layer 20b. The
first dielectric ceramic layer 20a is disposed between the first
internal electrode layer 21 and the second internal electrode layer
22. The second dielectric ceramic layer 20b is disposed in a region
where the internal electrode layers (21 and 22) are not disposed,
between the first dielectric ceramic layers 20a provided opposite
to each other with the internal electrode layer (21 and 22)
interposed therebetween.
[0059] The first external electrode 51 is provided on the first end
surface 15 of the multilayer body 10 and, in FIG. 1, includes a
portion which extends over a portion of each of the first main
surface 11, the second main surface 12, the first side surface 13
and the second side surface 14. The first external electrode 51 is
connected to the first internal electrode layer 21 at the first end
surface 15.
[0060] The second external electrode 52 is provided on the second
end surface 16 of the multilayer body 10 and, in FIG. 1, includes a
portion which extends over a portion of each of the first main
surface 11, the second main surface 12, the first side surface 13,
and the second side surface 14. The second external electrode 52 is
connected to the second internal electrode layer 22 at the second
end surface 16.
[0061] Each of the first external electrode 51 and the second
external electrode 52 preferably includes a Ni layer including Ni
and a ceramic material, for example. The Ni layer is a foundation
electrode layer (for example, base electrode layer). Such a Ni
layer can be formed by a cofiring method in which firing is
performed simultaneously with the first internal electrode layer 21
and the second internal electrode layer 22. The Ni layer is
preferably disposed directly on the multilayer body 10.
[0062] The first external electrode 51 preferably includes the Ni
layer, a first plated layer, and a second plated layer in order
from a side of the first end surface 15 of the multilayer body 10.
Similarly, the second external electrode 52 preferably includes the
Ni layer, the first plated layer, and the second plated layer in
order from a side of the second end surface 16 of the multilayer
body 10. The first plated layer is preferably formed by Ni plating,
and the second plated layer is preferably formed by Sn plating, for
example. Each of the first external electrode 51 and the second
external electrode 52 may include a conductive resin layer
including conductive particles and a resin between the Ni layer and
the first plated layer. Examples of the conductive particles in the
conductive resin layer include metal particles of Cu, Ag, and
Ni.
[0063] It should be noted that the Ni layer may be formed by a
so-called post-firing method which applies a conductive paste to
the end surface of the multilayer body, and then performs firing.
In this case, it may be unnecessary for the Ni layer to contain a
ceramic material.
[0064] Alternatively, each of the first external electrode 51 and
the second external electrode 52 may include a foundation electrode
layer including a metal such as Cu. The foundation electrode layer
may be formed by a cofiring method or a post-firing method.
Furthermore, the foundation electrode layer may include a plurality
of layers.
[0065] For example, the first external electrode 51 may have a
four-layer structure including a Cu layer as a foundation electrode
layer, a conductive resin layer including conductive particles and
a resin, the first plated layer, and the second plated layer in
order from a side of the first end surface 15 of the multilayer
body 10. Similarly, the second external electrode 52 may have, for
example, a four-layer structure including a Cu layer as a
foundation electrode layer, a conductive resin layer including
conductive particles and resin, the first plated layer, and the
second plated layer in order from a side of the second end surface
16 of the multilayer body 10.
[0066] As shown in FIGS. 3 and 4, the dielectric ceramic layer 20
includes the first dielectric ceramic layer 20a and the second
dielectric ceramic layer 20b. The first dielectric ceramic layer
20a is disposed between the first internal electrode layer 21 and
the second internal electrode layer 22. The second dielectric
ceramic layer 20b is disposed in a region where the internal
electrode layer is not disposed, between the first dielectric
ceramic layers 20a provided opposite to each other with the
internal electrode layer interposed therebetween.
[0067] As shown in FIGS. 2, 3 and 4, the multilayer body 10
includes an inner layer portion 30 in which the first internal
electrode layer 21 and the second internal electrode layer 22 are
provided opposite to each other with the dielectric ceramic layer
interposed therebetween, outer layer portions 31 and 32 sandwiching
the inner layer portion 30 in the stacking (T) direction, and a
third dielectric ceramic layers 41 and 42 sandwiching the inner
layer portion 30, the outer layer portion 31, and the outer layer
portion 32 in the width (W) direction. Third dielectric ceramic
layers 41 and 42 are also referred to as side margin portions. In
FIGS. 3 and 4, the inner layer portion is a region sandwiched
between the first internal electrode layer 21 closest to the first
main surface 11 and the first internal electrode layer 21 closest
to the second main surface 12 along the stacking (T) direction.
Although not shown, each of the outer layer portion 31 and the
outer layer portion 32 preferably includes a plurality of
dielectric ceramic layers 20 stacked in the stacking (T) direction,
and more preferably includes the first dielectric ceramic layer
20a.
[0068] The thickness of each of the outer layer portions 31 and 32
is preferably about 15 .mu.m or more and about 40 .mu.m or less,
for example. It should be noted that each of the outer layer
portions 31 and 32 may have a single layer structure rather than a
multi-layered structure.
[0069] As shown in FIG. 4, each of the third dielectric ceramic
layer 41 and the third dielectric ceramic layer 42 may include a
plurality of dielectric ceramic layers stacked in the width (W)
direction. Among the plurality of dielectric ceramic layers of the
third dielectric ceramic layers, the innermost layer in the width
direction is referred to as an inner layer, and the outermost layer
is referred to as an outer layer. The inner layer and the outer
layer have an interface therebetween. In FIG. 4, the third
dielectric ceramic layer 41 preferably has, as the dielectric
ceramic layer, a two-layer structure including an inner layer 41a
disposed innermost of the multilayer body 10, and an outer layer
41b disposed outermost of the multilayer body 10. Similarly, the
third dielectric ceramic layer 42 preferably has, as the dielectric
ceramic layer, a two-layer structure including an inner layer 42a
disposed innermost of the multilayer body 10, and an outer layer
42b disposed outermost of the multilayer body 10. It should be
noted that the third dielectric ceramic layer is not limited to a
two-layer structure, and may have a structure including three or
more layers. In a case in which the third dielectric ceramic layer
includes three or more dielectric ceramic layers, the dielectric
ceramic layer disposed innermost in the width direction is the
inner layer, and the dielectric ceramic layer disposed outermost in
the width direction is the outer layer. Furthermore, the number of
layers of the third dielectric ceramic layer of the first side
surface side of the multilayer body may be different from that of
the third dielectric ceramic layer of the second side surface side
of the multilayer body.
[0070] In a case in which the third dielectric ceramic layer is a
two-layer structure including an inner layer and an outer layer,
due to the difference in sinterability in the inner layer and the
outer layer, it is possible to confirm the two-layer structure and
the interface between the layers by observing with an optical
microscope in a dark field. The same applies to a case where the
third dielectric ceramic layer has a structure including three or
more layers.
[0071] The first dielectric ceramic layer 20a, the second
dielectric ceramic layer 20b, and the third dielectric ceramic
layers 41 and 42 are, for example, made of a dielectric ceramic
material mainly including BaTiO.sub.3 or the like. The dielectric
ceramic layer 20 of the inner layer portion 30 may further include
a sintering aid element.
[0072] The dielectric ceramic layer of the first dielectric ceramic
layer, the second dielectric ceramic layer, and the third
dielectric ceramic layer may include ceramic grains. Details of the
diameter of the ceramic grains will be described later.
[0073] In the multilayer ceramic capacitor according to the present
preferred embodiment, the composition of at least one dielectric
ceramic layer among the first dielectric ceramic layer, the second
dielectric ceramic layer, and the third dielectric ceramic layer is
different from the composition of the other dielectric ceramic
layers. The first dielectric ceramic layer, the second dielectric
ceramic layer, and the third dielectric ceramic layer each have a
different arrangement purpose or different characteristics required
for the manufacturing method. Therefore, by setting the composition
of at least one dielectric ceramic layer among the first dielectric
ceramic layer, the second dielectric ceramic layer, and the third
dielectric ceramic layer to be different from the composition of
the other dielectric ceramic layers, it is possible to achieve an
optimum composition according to the location where the dielectric
ceramic layer is disposed, making it possible to increase the
reliability.
[0074] In the multilayer ceramic capacitor according to the present
preferred embodiment, the composition of the first dielectric
ceramic layer may be different from the compositions of the second
dielectric ceramic layer and the third dielectric ceramic layer,
the composition of the second dielectric ceramic layer may be
different from the compositions of the first dielectric ceramic
layer and the third dielectric ceramic layer, the composition of
the third dielectric ceramic layer may be different from the
compositions of the first dielectric ceramic layer and the second
dielectric ceramic layer, and the composition of the first
dielectric ceramic layer, the composition of the second dielectric
ceramic layer, and the composition of the third dielectric ceramic
layer may be different from one another.
[0075] In the multilayer ceramic capacitor of the present preferred
embodiment, the composition of the second dielectric ceramic layer
and the composition of the third dielectric ceramic layer are
preferably different from each other, and the composition of the
first dielectric ceramic layer, the composition of the second
dielectric ceramic layer, and the composition of the third
dielectric ceramic layer are preferably different from one
another.
[0076] It should be noted that, in a case in which the third
dielectric ceramic layer includes a plurality of dielectric ceramic
layers, the plurality of dielectric ceramic layers of the third
dielectric ceramic layer may be the same composition relative to
each other, or may be different compositions from each other. In a
case in which any one composition of the plurality of dielectric
ceramic layers of the third dielectric ceramic layer is different
from that of the first dielectric ceramic layer, it can be
recognized that the composition of the third dielectric ceramic
layer is different from the composition of the first dielectric
ceramic layer. Furthermore, in a case in which any one composition
of the plurality of dielectric ceramic layers of the third
dielectric ceramic layer is different from that of the second
dielectric ceramic layer, it can be recognized that the composition
of the third dielectric ceramic layer is different from the
composition of the second dielectric ceramic layer.
[0077] Among the first dielectric ceramic layer, the second
dielectric ceramic layer, and the third dielectric ceramic layer,
it is preferable for the dielectric ceramic layers having different
compositions to have common main components and different types of
additives. Examples of the main component include BaTiO.sub.3,
CaTiO.sub.3, and SrTiO.sub.3. The additives preferably include
elements such as Si, Mg, Mn, Sn, Cu, rare earth, Ni and Al, for
example. The first dielectric ceramic layer, the second dielectric
ceramic layer, and the third dielectric ceramic layer may include
two or more of the above elements.
[0078] It should be noted that "the same composition" means that
the types of elements included in the dielectric ceramics included
in each dielectric ceramic layer are the same, and the content
(molar ratio) of all other elements based on Ti is within .+-.about
0.5%. It should be noted that the difference in diameter of the
ceramic grains included in each dielectric ceramic layer, and the
difference in porosity shall not be included in the difference in
the composition of the dielectric ceramic layer.
[0079] The composition of each of the dielectric ceramic layers can
be determined by performing an elemental analysis by wavelength
dispersive X-ray analysis (WDX) or transmission electron
microscopy-energy dispersive X-ray analysis (TEM-EDX) on an exposed
cut surface of a dielectric ceramic layer made by cutting a
multilayer ceramic capacitor. At this time, the composition of each
dielectric ceramic layer is measured at five locations to determine
the average value. The composition of the second dielectric ceramic
layer is measured at five locations from the second dielectric
ceramic layer exposed on the first end surface of the multilayer
body, and at five locations from the second dielectric ceramic
layer exposed on the second end surface of the multilayer body to
determine the average value. In a case in which the third
dielectric ceramic layer has a multi-layered structure, the
composition thereof is the sum of the compositions obtained by
multiplying the compositions obtained by measuring the composition
of each of the layers at five locations with the ratio of the
thickness of each of the layers occupied in the third dielectric
ceramic layer. It should be noted that, when segregation of
elements is observed in the vicinity of the interface with the
other dielectric ceramic layer or the internal electrode layer, the
portion where segregation of elements is observed shall not be the
measurement target of WDX.
[0080] The element to be added to the first dielectric ceramic
layer is preferably Mg, for example. The content of Mg in the first
dielectric ceramic layer is preferably about 0.05 mol % or more and
about 3.0 mol % or less, for example, with respect to 100 moles of
Ti. The content of Mg in the first dielectric ceramic layer is more
preferably less than the content of Mg in the second dielectric
ceramic layer and the third dielectric ceramic layer. When the
content of Mg in the first dielectric ceramic layer is small, since
the relative dielectric constant of the first dielectric ceramic
layer is increased, it is possible to improve the capacitance of
the multilayer ceramic capacitor. It should be noted that the
content of Mg in the first dielectric ceramic layer may preferably
be as low as possible.
[0081] The element to be added to the second dielectric ceramic
layer is preferably Sn, for example. The content of Sn in the
second dielectric ceramic layer is preferably about 0.05 mol % or
more, and about 3.0 mol % or less, for example, with respect to 100
moles of Ti. The content of Sn in the second dielectric ceramic
layer is preferably greater than the content of Sn in the first
dielectric ceramic layer and the third dielectric ceramic
layer.
[0082] The element to be added to the third dielectric ceramic
layer is preferably Si, for example. The content of Si in the third
dielectric ceramic layer is preferably about 0.05 mol % or more,
and about 5.0 mol % or less, for example, with respect to 100 moles
of Ti. The content of Si in the third dielectric ceramic layer is
preferably greater than the content of Si in the first dielectric
ceramic layer and the second dielectric ceramic layer. When the
content of Si in the third dielectric ceramic layer is large, since
the sinterability of the dielectric ceramic layer is increased, it
is possible to reduce or prevent the internal electrode layer from
being deteriorated due to the intrusion of water or the like from
the first side surface and the second side surface of the
multilayer body.
[0083] The element to be added to the third dielectric ceramic
layer is preferably Mg, for example. The content of Mg in the third
dielectric ceramic layer is preferably about 0.05 mol % or more and
about 5.0 mol % or less, for example with respect to 100 moles of
Ti. The content of Mg in the third dielectric ceramic layer is
preferably greater than the content of Mg in the first dielectric
ceramic layer and the second dielectric ceramic layer. When the
content of Mg in the third dielectric ceramic layer is large, it is
possible to reduce or prevent the grain growth of the ceramic
grains included in the third dielectric ceramic layer, and it is
possible to reduce or prevent a short circuit between the internal
electrode layers.
[0084] The element to be added to the third dielectric ceramic
layer is preferably Mn, for example. The content of Mn in the third
dielectric ceramic layer is preferably about 0.01 mol % or more,
and about 3.0 mol % or less, for example, with respect to 100 moles
of Ti. The content of Mn in the third dielectric ceramic layer is
preferably greater than the content of Mn in the first dielectric
ceramic layer and the second dielectric ceramic layer. When the
content of Mn in the third dielectric ceramic layer is large, it is
possible to reduce or prevent the grain growth of the ceramic
grains included in the third dielectric ceramic layer, and it is
possible to reduce or prevent a short circuit between the internal
electrode layers.
[0085] In the first dielectric ceramic layer, the second dielectric
ceramic layer, and the third dielectric ceramic layer, elements
other than the main component included in each dielectric ceramic
layer are preferably diffused into the other dielectric ceramic
layers. Furthermore, a portion of the elements included as an
additive in the first dielectric ceramic layer, the second
dielectric ceramic layer, and the third dielectric ceramic layer is
preferably diffused into the adjacent other dielectric ceramic
layers and the internal electrode layers.
[0086] FIG. 5 is a cross-sectional view taken along line B-B of the
multilayer ceramic capacitor shown in FIG. 1. It should be noted
that FIG. 5 is an LW cross-section of the multilayer ceramic
capacitor 1. As shown in FIG. 5, the second internal electrode
layer 22 is exposed on the second end surface 16 of the multilayer
body 10, and the second dielectric ceramic layer 20b is exposed on
the first end surface 15 of the multilayer body 10. Furthermore,
the third dielectric ceramic layer 41 and the third dielectric
ceramic layer 42 are respectively disposed on the first side
surface 13 side and the second side surface 14 side of the
multilayer body 10.
[0087] As shown in FIG. 5, there is an interface 2220b between the
second internal electrode layer 22 and the second dielectric
ceramic layer 20b. Furthermore, there are interfaces 2241 and 2242
between the second internal electrode layer 22 and the third
dielectric ceramic layers 41 and 42. Furthermore, there are
interfaces 20b41 and 20b42 between the second dielectric ceramic
layer 20b and the third dielectric ceramic layers 41 and 42.
[0088] In addition, although not shown in FIG. 5, the first
dielectric ceramic layer 20a is disposed on both sides in the
thickness direction of the second internal electrode layer 22 and
the second dielectric ceramic layer 20b. Therefore, it can be
recognized that the first dielectric ceramic layer 20a includes an
interface in direct contact with the second dielectric ceramic
layer 20b, the third dielectric ceramic layers 41 and 42, and the
internal electrode layers 21 and 22.
[0089] Furthermore, similarly to the second internal electrode
layer 22 shown in FIG. 5, the first internal electrode layer 21
also includes an interface in direct contact with the first
dielectric ceramic layer 20a, the second dielectric ceramic layer
20b, and the third dielectric ceramic layers 41 and 42.
[0090] In the first dielectric ceramic layer 20a, elements derived
from the second dielectric ceramic layer 20b may be segregated in
the vicinity of the interface with the second dielectric ceramic
layer 20b. Furthermore, in the first dielectric ceramic layer 20a,
elements originating from the third dielectric ceramic layer 41 or
42 may be segregated in the vicinity of the interface with the
third dielectric ceramic layer 41 or 42.
[0091] In the second dielectric ceramic layer 20b, elements
originating from the first dielectric ceramic layer 20a may be
segregated in the vicinity of the interface with the first
dielectric ceramic layers 20a. Furthermore, in the second
dielectric ceramic layer 20b, elements originating from the third
dielectric ceramic layer 41 or 42 may be segregated in the vicinity
of the interfaces 20b41 or 20b42 with the third dielectric ceramic
layer 41 or 42.
[0092] In the third dielectric ceramic layers 41 and 42, elements
originating from the first dielectric ceramic layer 20a may be
segregated in the vicinity of the interface with the first
dielectric ceramic layer 20a. Furthermore, in the third dielectric
ceramic layers 41 and 42, elements originating from the second
dielectric ceramic layer 20b may be segregated in the vicinity of
the interfaces 20b41 and 20b42 with the second dielectric ceramic
layer 20b.
[0093] In the first internal electrode layer 21 and the second
internal electrode layer 22, elements originating from the first
dielectric ceramic layer 20a may be segregated in the vicinity of
the interface with the first dielectric ceramic layer 20a. In
addition, in the first internal electrode layer 21 and the second
internal electrode layer 22, elements originating from the second
dielectric ceramic layer 20b may be segregated in the vicinity of
the interface 2220b with the second dielectric ceramic layer 20b.
Furthermore, in the first internal electrode layer 21 and the
second internal electrode layer 22, elements originating from the
third dielectric ceramic layers 41 and 42 may be segregated in the
vicinity of the interfaces 2241 and 2242 with the third dielectric
ceramic layers 41 and 42. In addition, both the element originating
from the second dielectric ceramic layer 20b and the element
originating from the third dielectric ceramic layer 41 or 42 may be
segregated in the vicinity of the portion where the interface 2220b
between the second internal electrode layer 22 and the second
dielectric ceramic layer 20b, and the interface 2241 or 2242
between the second internal electrode layer 22, and the third
dielectric ceramic layer 41 or 42 are in contact with each other
(the corner of the second internal electrode layer 22 on the first
end surface 15 side).
[0094] The porosity of the first dielectric ceramic layer, the
second dielectric ceramic layer, and the third dielectric ceramic
layer may be the same as, or may be different from one another. A
multilayer ceramic capacitor is cut, and the cut surface, which
exposes each dielectric ceramic layer, is observed by a scanning
electron microscope (SEM) at 20,000 times magnification. An area
having a visual field size of about 6.3 .mu.m.times.about 4.4 .mu.m
is photographed at five locations so that the areas do not overlap
each other, and the ratio of the area occupied by the voids to the
entire visual field is calculated as the porosity by image analysis
from each of the obtained SEM images, and an average value in the
five visual fields is obtained. However, in a case in which the
third dielectric ceramic layer includes a plurality of layers, the
porosity of the third dielectric ceramic layer is calculated as the
sum of the product of porosity of each layer and the value obtained
by dividing the thickness of the layer by the thickness of the
third dielectric ceramic layer after obtaining the porosity of each
layer individually.
[0095] The first dielectric ceramic layer, the second dielectric
ceramic layer, and the third dielectric ceramic layer preferably
include ceramic grains. When the dielectric ceramic layer includes
ceramic grains, interfacial resistance occurs at the interface
between the ceramic grains, a result of which the insulation
resistance between the internal electrode layers increases, making
it possible to reduce or prevent the occurrence of a short
circuit.
[0096] A rare earth element is preferably present at the interface
of the ceramic grains. The presence of a rare earth element at the
interface of the ceramic grains can be confirmed by elemental
analyses with TEM-EDX. Examples of the rare earth elements include
La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, and Y. The
presence of a rare earth element at the interface of the ceramic
grains allows for further increase of the interfacial resistance of
the dielectric ceramic layer, as a result of which it is possible
to further improve the reliability of the multilayer ceramic
capacitor. It should be noted that Mg, Mn, Si or the like may also
be present.
[0097] The rare earth element is preferably present in an amount of
about 0.2 mol % or more and about 5 mol % or less, for example,
with respect to 100 moles of Ti. Herein, 100 moles of Ti defines
the amount of rare earth element with respect to 100 moles of Ti on
the assumption that the dielectric ceramic material of the
dielectric ceramic layers has a compound having a perovskite
structure (structure represented by ABO.sub.3, B.dbd.Ti) as a main
component. The amount of rare earth element can be confirmed by
TEM-EDX.
[0098] In the multilayer ceramic capacitor, the thickness of each
of the first internal electrode layer and the second internal
electrode layer is preferably about 0.4 .mu.m or less, for example.
Furthermore, the thickness of each of the first internal electrode
layer and the second internal electrode layer is preferably about
0.38 .mu.m or less, for example. Furthermore, the thickness of each
of the first internal electrode layer and the second internal
electrode layer is preferably about 0.25 .mu.m or more, for
example.
[0099] The thickness of the first dielectric ceramic layer is
preferably about 0.55 .mu.m or less, for example. Furthermore, the
thickness of the first dielectric ceramic layer is preferably about
0.4 .mu.m or more, for example.
[0100] The thickness of the second dielectric ceramic layer is
preferably the same or substantially the same as the thickness of
the internal electrode layer.
[0101] The thickness of each of the third dielectric ceramic layers
41 and 42 is preferably about 5 .mu.m or more and about 40 .mu.m or
less, and more preferably about 5 .mu.m or more and about 20 .mu.m
or less, for example. The thicknesses of the third dielectric
ceramic layers 41 and 42 are preferably the same or substantially
the same. However, the outer layer 41b is preferably thicker than
the inner layer 41a, while the inner layer 41a and the outer layer
41b satisfy the above range. Similarly, the outer layer 42b is
preferably thicker than the inner layer 42a, while the inner layer
42a and the outer layer 42b satisfy the above range.
[0102] From the viewpoint of maintaining the shape and performance
of the multilayer ceramic capacitor 1, the inner layer 41a is
preferably thinner than the outer layer 41b. Similarly, the inner
layer 42a is preferably thinner than the outer layer 42b.
[0103] The thickness of each of the inner layers 41a and 42a is
preferably about 0.1 .mu.m or more and about 20 .mu.m or less, for
example. The inner layers 41a and 42a preferably have the same or
substantially the same thickness.
[0104] The thickness of each of the outer layers 41b and 42b is
preferably about 5 .mu.m or more and about 20 .mu.m or less, for
example. The outer layers 41b and 42b have preferably the same or
substantially the same thickness.
[0105] The thickness of each ceramic layer of the side margin
portion indicates an average value when the thickness of the third
dielectric ceramic layer along the stacking (T) direction is
measured at a plurality of locations.
Method for Manufacturing a Multilayer Ceramic Capacitor
[0106] A method for manufacturing a multilayer ceramic capacitor
according to a preferred embodiment of the present invention
includes preparing a green chip, the green chip including a
multilayer structure including a plurality of first dielectric
ceramic layers, a plurality of second dielectric ceramic layers,
and a plurality of pairs of first internal electrode layers and
second internal electrode layers in an unfired state, the first
internal electrode layers and the second internal electrode layers
being exposed on a first side surface and a second side surface on
opposite sides in a width direction orthogonal or substantially
orthogonal to a stacking direction; forming an unfired third
dielectric ceramic layer on the first side surface and the second
side surface of the green chip, and thus fabricating an unfired
multilayer body; and firing the unfired multilayer body, in which
the preparing of the green chip further includes stacking a ceramic
green sheet obtained by forming an unfired first internal electrode
layer or an unfired second internal electrode layer on a surface of
the unfired first dielectric ceramic layer and forming an unfired
second dielectric ceramic layer in a region where the first
internal electrode layer and the second internal electrode layer
are not provided, in which the fabricating the unfired multilayer
body further includes forming an unfired side margin portion by
forming an unfired inner layer on the first side surface and the
second side surface and forming an unfired outer layer on an
outermost side, and in which a composition of at least one
dielectric ceramic layer among the first dielectric ceramic layer,
the second dielectric ceramic layer, and the third dielectric
ceramic layer is different from that of the other dielectric
ceramic layers.
[0107] A non-limiting example of a method for manufacturing the
multilayer ceramic capacitor 1 shown in FIG. 1 will be described
below.
[0108] First, a ceramic green sheet is prepared which is to be
provided with the first dielectric ceramic layer 20a, the second
dielectric ceramic layer 20b, and the third dielectric ceramic
layers 41 and 42. The ceramic green sheet includes a binder, a
solvent, and the like, in addition to a ceramic raw material
including the dielectric ceramic material described above.
Furthermore, an additive including a rare earth element may be
added to the ceramic raw material. By changing the element included
in the additive, the compositions of the first dielectric ceramic
layer, the second dielectric ceramic layer, and the third
dielectric ceramic layer can be changed. The ceramic raw materials
as a main component are preferably the same or substantially the
same. The ceramic green sheet is molded using, for example, a die
coater, a gravure coater, a micro gravure coater, or the like, on a
carrier film.
[0109] FIGS. 6, 7, and 8 are plan views schematically showing an
example of a ceramic green sheet. FIGS. 6, 7, and 8 respectively
show a first ceramic green sheet 101 for forming the inner layer
portion 30, a second ceramic green sheet 102 for forming the inner
layer portion 30, and a third ceramic green sheet 103 for forming
the outer layer portion 31 or 32.
[0110] In FIGS. 6, 7, and 8, the first ceramic green sheet 101, the
second ceramic green sheet 102, and the third ceramic green sheet
103 are not separated into each multilayer ceramic capacitor 1. In
FIGS. 6, 7, and 8, the cutting lines X and Y at the time of
separating into each multilayer ceramic capacitor 1 are shown. The
cutting line X is parallel or substantially parallel to the length
(L) direction, and the cutting line Y is parallel or substantially
parallel to the width (W) direction.
[0111] As shown in FIG. 6, in the first ceramic green sheet 101, an
unfired first internal electrode layer 121 corresponding to the
first internal electrode layer 21 is formed on an unfired first
dielectric ceramic layer 120a corresponding to the first dielectric
ceramic layer 20a. Furthermore, an unfired second dielectric
ceramic layer 120b corresponding to the second dielectric ceramic
layer 20b is formed in a region where the unfired first internal
electrode layer 121 is not formed. The unfired first dielectric
ceramic layer 120a and the unfired second dielectric ceramic layer
120b also refer to an unfired dielectric ceramic layer 120
corresponding to the dielectric ceramic layer 20.
[0112] As shown in FIG. 7, in the second ceramic green sheet 102,
an unfired second internal electrode layer 122 corresponding to the
second internal electrode layer 22 is formed on the unfired first
dielectric ceramic layer 120a corresponding to the first dielectric
ceramic layer 20a. Furthermore, the unfired second dielectric
ceramic layer 120b corresponding to the second dielectric ceramic
layer 20b is formed in a region where the unfired second internal
electrode layer 122 is not formed. The unfired first dielectric
ceramic layer 120a and the unfired second dielectric ceramic layer
120b also refer to the unfired dielectric ceramic layer 120
corresponding to the dielectric ceramic layer 20.
[0113] The method for fabricating the first ceramic green sheet 101
shown in FIG. 6 and the second ceramic green sheet shown in FIG. 7
is not particularly limited. However, examples thereof include a
method for applying a dielectric paste as the mixture of a
dielectric ceramic and a solvent, which becomes the second
dielectric ceramic layer 20b by firing, and a conductive paste,
which becomes the internal electrode layer 21 or 22 by firing,
respectively to predetermined regions of the surface of the unfired
first dielectric ceramic layer 120a. The order in which the
dielectric paste and the conductive paste are applied is not
particularly limited, and the conductive paste may be applied after
the dielectric paste is applied first, or the dielectric paste may
be applied after the conductive paste is applied first. In
addition, the dielectric paste and the conductive paste may be
applied so that a portion of the surface of the paste applied
previously is covered with a portion of the paste applied
later.
[0114] As shown in FIG. 8, the third ceramic green sheet 103
corresponding to the outer layer portion 31 or 32 includes the
unfired first dielectric ceramic layer 120a corresponding to the
first dielectric ceramic layer, and neither the unfired internal
electrode layer 121 or 122 nor the unfired second dielectric
ceramic layer 120b is formed.
[0115] The first internal electrode layer 121 and the second
internal electrode layer 122 can be formed using any conductive
paste. For example, a screen-printing method, a gravure printing
method, or the like can be used for forming the first internal
electrode layer 121 and the second internal electrode layer 122
using the conductive paste.
[0116] The first internal electrode layer 121 and the second
internal electrode layer 122 are disposed over two regions which
are partitioned by the cutting line Y and are adjacent to each
other in the length (L) direction, and extend in a strip shape in
the width (W) direction. The regions partitioned by the cutting
line Y of the first internal electrode layer 121 and the second
internal electrode layer 122 are shifted from each other in the
length (L) direction by one row. That is, the cutting line Y
passing through the center of the first internal electrode layer
121 passes through a region between the second internal electrode
layers 122 (i.e., the center of the second dielectric ceramic layer
120b), and the cutting line Y passing through the center of the
second internal electrode layer 122 passes through the region
between the first internal electrode layers 121 (i.e., the center
of the second dielectric ceramic layer 120b).
[0117] Thereafter, the first ceramic green sheet 101, the second
ceramic green sheet 102, and the third ceramic green sheet 103 are
stacked, thus fabricating a mother block.
[0118] FIG. 9 is an exploded perspective view schematically showing
an example of the mother block. In FIG. 9, for convenience of
explanation, the first ceramic green sheet 101, the second ceramic
green sheet 102, and the third ceramic green sheet 103 are shown in
an exploded manner. However, in an actual mother block 104, the
first ceramic green sheet 101, the second ceramic green sheet 102,
and the third ceramic green sheet 103 are integrally crimped by
hydrostatic pressing, or the like, for example.
[0119] In the mother block 104 shown in FIG. 9, the first ceramic
green sheet 101 and the second ceramic green sheet 102
corresponding to the inner layer portion 30 are alternately stacked
in the stacking (T) direction. Furthermore, the third ceramic green
sheets 103 corresponding to the outer layer portions 31 and 32 are
stacked on the upper and lower surfaces in the stacking (T)
direction of the first ceramic green sheets 101 and the second
ceramic green sheets 102 which are alternately stacked. It should
be noted that, although the third ceramic green sheet 103 is
configured such that three pieces of the first dielectric ceramic
layer 120a are stacked in FIG. 9, the number of first dielectric
ceramic layers 120a to be stacked can be changed as
appropriate.
[0120] By cutting the resulting mother block 104 along the cutting
lines X and Y (refer to FIGS. 6, 7, and 8), a plurality of green
chips are fabricated. For this cutting, a method such as dicing,
push cutting, or laser cutting is applied, for example.
[0121] FIG. 10 is a perspective view schematically showing an
example of a green chip. The green chip 110 shown in FIG. 10 has a
multilayer structure including the plurality of first dielectric
ceramic layers 120a and the plurality of second dielectric ceramic
layers 120b, and the plurality of pairs of first internal electrode
layers 121 and second internal electrode layers 122 in an unfired
state. A first side surface 113 and a second side surface 114 of
the green chip 110 are planes provided by cutting along the cutting
line X, and a first end surface 115 and a second end surface 116
are planes provided by cutting along the cutting line Y. The first
internal electrode layer 121 and the second internal electrode
layer 122 are exposed on the first side surface 113 and the second
side surface 114. Furthermore, only the first internal electrode
layers 121 and the second dielectric ceramic layer 120b are exposed
on the first end surface 115, and only the second internal
electrode layer 122 and the second dielectric ceramic layer 120b
are exposed on the second end surface 116. The first dielectric
ceramic layer 120a is exposed on the first side surface 113, the
second side surface 114, the first end surface 115, and the second
end surface 116. However, the locations of the second dielectric
ceramic layers that are exposed in a region to be disposed differ.
In other words, the second dielectric ceramic layers 120b disposed
at a side of the first end surface 115 is not exposed on the second
end surface 116, and the second dielectric ceramic layer 120b
disposed at a side of the second end surface 116 is not exposed on
the first end surface 115.
[0122] An unfired third dielectric ceramic layer is formed on the
first side surface 113 and the second side surface 114 of the
resulting green chip 110, as a result of which an unfired
multilayer body is fabricated. The unfired third dielectric ceramic
layer is formed, for example, by pasting a ceramic green sheet made
of a dielectric ceramic on the first side surface and the second
side surface of the green chip.
[0123] For example, in a case in which the third dielectric ceramic
layer includes two layers of the inner layer and the outer layer,
first, in order to fabricate a ceramic green sheet for the inner
layer, a ceramic slurry is produced which includes a binder, a
solvent, and the like, in addition to the ceramic raw material
including a dielectric ceramic material mainly including
BaTiO.sub.3 or the like. Si as a sintering aid may be added to the
ceramic slurry for the inner layer. The inner layer has a function
of adhering to the green chip 110. In addition, a liquid phase
metal may be added to the ceramic slurry for the inner layer, and
more rare earth elements, Mg, and Mn may be added to the ceramic
slurry for the inner layer than to the ceramic green sheet for
forming the inner layer portion. Thus, it is possible to reduce or
prevent the grain growth of the ceramic grains included in the
dielectric ceramic layer sandwiched by the width direction ends of
the internal electrode layers.
[0124] Next, in order to fabricate a ceramic green sheet for the
outer layer, a ceramic slurry including a binder, a solvent, and
the like in addition to a ceramic raw material including a
dielectric ceramic material including BaTiO.sub.3 or the like as a
main component is produced. In addition, Si as a sintering aid may
be added to the ceramic slurry for the outer layer. Furthermore, Si
included in the ceramic green sheet for the inner layer is
preferably larger than Si included in the ceramic green sheet for
the outer layer. The degree of the content is determined based on
the size of the area of a region where Si is detected, by imaging
the cross-section by WDX.
[0125] The ceramic slurry for the outer layer is applied to the
surface of a resin film and dried, such that the ceramic green
sheet for the outer layer is formed. The ceramic slurry for the
inner layer is applied to the surface of the ceramic green sheet
for the outer layer on the resin film and dried, such that the
ceramic green sheet for the inner layer is formed. As described
above, a ceramic green sheet having a two-layer structure is
obtained.
[0126] It should be noted that the ceramic green sheet having the
two-layer structure can also be obtained, for example, by forming
the ceramic green sheet for the outer layer and the ceramic green
sheet for the inner layer in advance, and then bonding them to each
other. Furthermore, the ceramic green sheet is not limited to the
two-layer structure, and may have a structure with three or more
layers.
[0127] Thereafter, the ceramic green sheet is peeled from the resin
film.
[0128] Subsequently, the ceramic green sheet for the inner layer of
the ceramic green sheet and the first side surface 113 of the green
chip 110 are made to face each other, and pressed and punched, thus
forming the unfired side margin portion 41. Furthermore, the
ceramic green sheets for the inner layer of the ceramic green sheet
and the second side surface 114 of the green chip 110 are also made
to face each other, and pressed and punched, thus forming the
unfired side margin portion 42. At this time, an organic solvent
defining and functioning as an adhesive is preferably applied to
the side surface of the green chip in advance. As described above,
an unfired multilayer body is obtained.
[0129] It is preferable to perform barrel polishing or the like,
for example, on the unfired multilayer body obtained by the above
method. By polishing the unfired multilayer body, the corners and
ridges of a fired multilayer body 10 are rounded.
[0130] Thereafter, in the unfired multilayer body, a conductive
paste for an external electrode including Ni and a ceramic material
is applied on each end surface of the first end surface 115 and the
second end surface 116 of the green chip 110.
[0131] The conductive paste for the external electrode preferably
includes, as a ceramic material, the same or substantially the same
dielectric ceramic material as the first dielectric ceramic layer,
the second dielectric ceramic layer, or the outer layer. The
content of the ceramic material in the conductive paste for the
external electrodes is preferably about 15% by weight or more, for
example. Furthermore, the content of the ceramic material in the
conductive paste for the external electrode is preferably about 25%
by weight or less, for example.
[0132] Next, the unfired multilayer body to which the conductive
paste for the external electrode is subjected to, for example, a
degreasing treatment in a nitrogen atmosphere under a predetermined
condition, and then the resulting multilayer body is fired at a
predetermined temperature in a nitrogen-hydrogen-water vapor mixed
atmosphere. Thus, the unfired multilayer body and the conductive
paste for the external electrode are fired simultaneously, and the
multilayer body 10, the Ni layer connected to the first internal
electrode layer 21, and the Ni layer connected to the second
internal electrode layer 22 are formed at the same time by a
cofiring method. Thereafter, the first plated layer including Ni
plating and the second plated layer including Sn plating are
stacked in this order on the surface of each of the Ni layer. Thus,
the first external electrode 51 and the second external electrode
52 are formed.
[0133] It should be noted that on the multilayer body 10, the first
external electrode 51 and the second external electrode 52 may be
formed at separate timings by a post-firing method. Specifically,
first, a multilayer body 10 is formed by performing a degreasing
treatment on an unfired laminate under a predetermined condition in
a nitrogen atmosphere, for example, and then firing the multilayer
body at a predetermined temperature in a nitrogen-hydrogen-water
vapor mixed atmosphere. Then, on each end surface of the first end
surface 15 and the second end surface 16 of the multilayer body 10,
a conductive paste including Cu powder is applied and baked. Thus,
a foundation electrode layer connected to the first internal
electrode layer 21 and a foundation electrode layer connected to
the second internal electrode layer 22 are formed. Then, on the
surface of each of the underlying electrode layer, conductive
particles (e.g., Cu, Ag, Ni, metal particles such as) and a
conductive resin layer including a resin, a first plated layer
including Ni plating, and a second plated layer including Sn
plating are laminated in this order. Thus, the first external
electrode 51 and the second external electrode 52 are formed.
[0134] Thus, the multilayer ceramic capacitor 1 is
manufactured.
[0135] In the preferred embodiment described above, the unfired
third dielectric ceramic layer preferably is formed on both sides
of the green chip after obtaining the plurality of green chips by
cutting the mother block 104 along the cutting lines X and Y, for
example. However, the following modifications are also
possible.
[0136] That is, it may be configured such that a plurality of
rod-shaped green block bodies are obtained which are provided by
cutting the mother block along only the cutting line X and in which
the first internal electrode layer and the second internal
electrode layer are exposed on the side surface provided by cutting
along the cutting line X, and thereafter, the unfired third
dielectric ceramic layer is formed on both sides of the green block
bodies to obtain a plurality of unfired multilayer bodies by
cutting along the cutting line Y, followed by the unfired
multilayer bodies being fired. By performing the same steps as in
the above-described preferred embodiment after firing, a multilayer
ceramic capacitor can be manufactured.
[0137] Preferred embodiments of the present invention further
include the following configurations of (1) to (7).
[0138] (1) Alloy Portion Between the Dielectric Ceramic Layer and
the Internal Electrode Layer and the External Electrode
[0139] In a multilayer ceramic capacitor 1 according to a preferred
embodiment of the present invention, as shown in FIG. 11, a second
alloy portion 320 is provided between the second dielectric ceramic
layer 20b and the first internal electrode layer 21, and between
the second dielectric ceramic layer 20b and the second internal
electrode layer 22, respectively. Furthermore, in the multilayer
ceramic capacitor 1, a first alloy portion 310 is provided between
the first dielectric ceramic layer 20a and the first internal
electrode layer 21, and between the first dielectric ceramic layer
20a and the second internal electrode layer 22, respectively.
[0140] As shown in FIG. 12, metal elements 321a are segregated at
the interface 2220b with the second dielectric ceramic layer 20b in
the second internal electrode layer 22. The second alloy portion
320 includes a segregation layer 321 which is a layer segregation
by the metal elements 321a. Similarly to this, the metal elements
321a are segregated to provide the segregation layer 321 also at
the interface 2220b with the second dielectric ceramic layer 20b in
the first internal electrode layer 21, and the second alloy portion
320 by the segregation layer 321 is provided. The second alloy
portion 320 is provided on the surfaces of the first internal
electrode layer 21 and the second internal electrode layer 22
closer to the second dielectric ceramic layer 20b, respectively.
The second alloy portion 320 is provided between the first internal
electrode layer 21 and the second dielectric ceramic layer 20b, and
between the second internal electrode layer 22 and the second
dielectric ceramic layer 20b.
[0141] Furthermore, as shown in FIG. 12, metal elements 311a are
segregated at an interface 2220a with the first dielectric ceramic
layer 20a in the second internal electrode layer 22. The first
alloy portion 310 includes a segregation layer 311 which is a layer
segregation by the metal element 311a. Similarly to this, the metal
elements 311a are segregated to provide the segregation layer 311
at the interface 2220a with the first dielectric ceramic layer 20a
in the first internal electrode layer 21, and the first alloy
portion 310 by the segregation layer 311 is provided. The first
alloy portion 310 is provided on the surfaces of the first internal
electrode layer 21 and the second internal electrode layer 22
closer to the first dielectric ceramic layer 20a, respectively. The
first alloy portion 310 is provided between the first internal
electrode layer 21 and the first dielectric ceramic layer 20a, and
between the second internal electrode layer 22 and the first
dielectric ceramic layer 20a.
[0142] There are a plurality of types of segregated metal elements
321a in the second alloy portion 320. The plurality of types of
metal elements 321a in the segregation layer 321 includes a metal
element provided in a greatest amount among the metal elements of
the first internal electrode layer 21 and the second internal
electrode layer 22, and an element derived from the second
dielectric ceramic layer 20b. Furthermore, the same applies to the
segregated metal element 311a of the first alloy portion 310. That
is, the metal element 311a includes a metal element provided in a
greatest amount among the metal elements of the first internal
electrode layer 21 and the second internal electrode layer 22, and
an element derived from the first dielectric ceramic layer 20a.
[0143] Examples of the metal element provided in a greatest amount
among the metal elements of the first internal electrode layer 21
and the second internal electrode layer 22 include one of Ni, Cu,
Ag, Pd, Au, and Pt. On the other hand, examples of the element
derived from the second dielectric ceramic layer 20b and the first
dielectric ceramic layer 20a include a metal element as an
additive. More specifically, examples thereof include any one or
more metal elements among the metal group of Sn, In, Ga, Zn, Bi,
Pb, Cu, Ag, Pd, Pt, Ph, Ir, Ru, Os, Fe, V, Y, and Ge, among which,
Sn, Ga, and Ge is particularly preferred. Hereinafter, this metal
group may be referred to as a metal group M.
[0144] The segregation of the metal element 321a occurs when the
metal element included in the second dielectric ceramic layer 20b
migrates to the first internal electrode layer 21 and the second
internal electrode layer 22 during firing of the second dielectric
ceramic layer 20b. Furthermore, the segregation of the metal
element 311a occurs when the metal element included in the first
dielectric ceramic layer 20a migrates to the first internal
electrode layer 21 and the second internal electrode layer 22
during firing of the first dielectric ceramic layer 20a.
[0145] In a case in which the first dielectric ceramic layer 20a
includes BaTiO.sub.3 as a main component, the second alloy portion
320 has a higher content of metal elements included in the second
dielectric ceramic layer 20b, i.e. any one or more of the above
metal group M in terms of molar ratio relative to 100 moles of Ti,
than the first alloy portion 310.
[0146] FIG. 13 shows a plane of the multilayer body 10 including a
central portion in the width (W) direction, and the length (L)
direction and the stacking (T) direction. In the multilayer ceramic
capacitor 1, in the plane shown in FIG. 13, the first internal
electrode layer 21 includes a plurality of first interspersed
internal electrodes 210 interspersed discontinuously in the length
(L) direction at the end in the length (L) direction that is not
connected to the second external electrode 52. Furthermore, the
second internal electrode layer 22 includes a plurality of second
interspersed internal electrodes 220 interspersed discontinuously
in the length (L) direction at the end in the length (L) direction
that is not connected to the first external electrode 51. Each of
the first interspersed internal electrodes 210 and the second
interspersed internal electrodes 220 is provided within the second
dielectric ceramic layer 20b. The plurality of first interspersed
internal electrodes 210 may be connected to the first internal
electrode layer 21 while extending in the width (W) direction.
Furthermore, the plurality of second interspersed internal
electrodes 220 may also be connected to the second internal
electrode layer 22 while extending in the width (W) direction.
[0147] A fourth alloy portion 340 is provided around each of the
first interspersed internal electrode 210 and the second
interspersed internal electrode 220. The fourth alloy portion 340
is defined by a segregation layer 341 which is a layer segregation
by the metal element 341a. The metal element 341a includes a metal
element provided in a greatest amount among the metal elements of
the first internal electrode layer 21 and the second internal
electrode layer 22, and one or more kinds of metal elements among
the metal group M originating from the second dielectric ceramic
layer 20b.
[0148] The segregation of the metal element 341a occurs when the
metal element included in the second dielectric ceramic layer 20b
migrates to the first interspersed internal electrode 210 and the
second interspersed internal electrode 220 during firing of the
second dielectric ceramic layer 20b. It should be noted that the
segregation of the metal element 341a occurs around one or a
plurality of the first interspersed internal electrodes 210 and one
or a plurality of the second interspersed internal electrodes 220.
Alternatively, the segregation of the metal element 341a may occur
around the entire or substantially the entire periphery of the
first interspersed internal electrode 210 and around the entire or
substantially the entire periphery of the second interspersed
internal electrode 220.
[0149] As shown in FIG. 14, in the multilayer ceramic capacitor 1,
a third alloy portion 330 is provided between the third dielectric
ceramic layers 41 and 42 and the first internal electrode layer 21,
and between the third dielectric ceramic layers 41 and 42 and the
second internal electrode layer 22, respectively.
[0150] As shown in FIG. 14, a metal element 331a is segregated at
an interface 2220c between the first internal electrode layer 21
and the third dielectric ceramic layers 41 and 42. Furthermore, the
metal element 331a is also segregated at the interface 2220c with
the third dielectric ceramic layers 41 and 42 in the second
internal electrode layer 22. The third alloy portion 330 provided
by a layer segregation by the metal element 331a, i.e. a
segregation layer 331. The third alloy portions 330 are provided on
the surfaces of the first internal electrode layer 21 and the
second internal electrode layer 22, closer to the third dielectric
ceramic layer 41 and 42, respectively. The third alloy portions 330
are provided between the first internal electrode layer 21 and the
third dielectric ceramic layers 41 and 42, and between the second
internal electrode layer 22 and the third dielectric ceramic layers
41 and 42, respectively.
[0151] The metal element 331a includes a metal element provided in
a greatest amount among the metal elements of the first internal
electrode layer 21 and the second internal electrode layer 22, and
one or more kinds of metal elements among the metal group M
originating from the third dielectric ceramic layers 41 and 42.
Examples of the elements originating from the third dielectric
ceramic layers 41 and 42 include a metal element as an additive.
More specifically, examples thereof include any one or more of
metal elements among the above metal group M.
[0152] The segregation of the metal element 331a occurs when the
metal element included in the third dielectric ceramic layers 41
and 42 migrates to the first internal electrode layer 21 and the
second internal electrode layer 22 during firing of the third
dielectric ceramic layers 41 and 42.
[0153] In the multilayer ceramic capacitor 1, the first external
electrode 51 and the second external electrode 52 each include a Ni
layer as a foundation electrode layer, and, when formed by a
cofiring method, as shown in FIG. 15, a fifth alloy portion 350 is
formed in the Ni layer.
[0154] FIG. 15 shows a state in which the fifth alloy portion 350
is provided at an interface 51b with the second dielectric ceramic
layer 20b in the first external electrode 51. The fifth alloy
portion 350 is a segregation layer 351 which is a layer segregation
by a metal element 351a. Similarly to this, the fifth alloy portion
350 due to the segregation of the metal element 351a is also
provided at the interface 51b with the second dielectric ceramic
layer 20b in the second external electrode 52. The segregation of
the metal element 351a occurs when the metal element included in
the second dielectric ceramic layer 20b migrates to the first
external electrode 51 and the second external electrode 52 during
firing of the second dielectric ceramic layer 20b.
[0155] It should be noted that, in the multilayer body 10 of the
multilayer ceramic capacitor 1 of the present preferred embodiment,
the ends of the first internal electrode layer 21, the second
internal electrode layer 22, and the second dielectric ceramic
layer 20b which are adjacent to each other may overlap with each
other. For example, as shown in FIG. 16, the end of the second
dielectric ceramic layer 20b may be superimposed on the end of the
second internal electrode layer 22. Furthermore, as shown in FIG.
17, the end of the second dielectric ceramic layer 20b may overlap
the end of the first internal electrode layer 21. In such a
configuration in which the ends overlap with each other, the first
internal electrode layer 21 and the second internal electrode layer
22 may be superimposed on the second dielectric ceramic layer
20b.
[0156] In the multilayer ceramic capacitor 1 of the present
preferred embodiment, the second alloy portion 320, which includes
one metal element provided in a greatest amount among the metal
elements of the internal electrode layer, and any one or more metal
elements among the metal group M including Sn, In, Ga, Zn, Bi, Pb,
Cu, Ag, Pd, Pt, Ph, Ir, Ru, Os, Fe, V, and Y, is provided between
the second dielectric ceramic layer 20b and the first internal
electrode layer 21, and between the second dielectric ceramic layer
20b and the second internal electrode layer 22, respectively.
[0157] The electric field is likely to be concentrated at the
respective ends of the first internal electrode layer 21 and the
second internal electrode layer 22 in contact with the second
dielectric ceramic layer 20b. For this reason, there is a
possibility of lowering the reliability of a multilayer ceramic
capacitor. However, according to the multilayer ceramic capacitor 1
of the present preferred embodiment, the second alloy portion 320
is provided between the second dielectric ceramic layer 20b, and
the first internal electrode layer 21 and the second internal
electrode layer 22, such that it is possible to reduce or prevent
the electric field concentration, thus improving the
reliability.
[0158] In the multilayer ceramic capacitor 1 of the present
preferred embodiment, in a case in which the first dielectric
ceramic layer 20a includes Ba and Ti, the first alloy portion 310,
which includes a metal element provided in a greatest amount among
the metal elements of the internal electrode layer, and any one or
more of metal elements among the above metal group M, is provided
between the first dielectric ceramic layer 20a and the first
internal electrode layer 21, and between the first dielectric
ceramic layer 20a and the second internal electrode layer 22,
respectively. The second alloy portion 320 has a higher content of
the above metal group M in terms of molar ratio relative to 100
moles of Ti than the first alloy portion 310.
[0159] Thus, it is possible for the second alloy portion 320 to
reduce or prevent the electric field concentration occurring at a
portion in the vicinity of the interfaces with the second
dielectric ceramic layer 20b in the first internal electrode layer
21 and the second internal electrode layer 22, thus improving the
reliability. Furthermore, by increasing the content of the metal
group M of the second alloy portion 320, which is provided at the
ends of the first internal electrode layer 21 and the second
internal electrode layer 22 in contact with the second dielectric
ceramic layer 20b where electric field concentration is likely to
occur, in terms of molar ratio relative to 100 moles of Ti, more
than the first alloy portion 310 provided closer to the first
dielectric ceramic layer 20a, it is possible to effectively reduce
the electric field concentration on the second dielectric ceramic
layer 20b side, thus further improving the reliability.
[0160] By the amount of metal of the metal group M added to each of
the first dielectric ceramic layer 20a and the second dielectric
ceramic layer 20b being controlled, the thickness of the first
alloy portion 310 and the second alloy portion 320, and the
concentration of the metal group M included therein can be
controlled. For example, when the concentration of the metal group
M added to the second dielectric ceramic layer 20b is higher than
that of the first dielectric ceramic layer 20a, as shown in FIG.
12, the thickness of the second alloy portion 320 increases, or the
concentration of the metal group M increases as it approaches the
second dielectric ceramic layer 20b, or in some cases, the
thickness of the second alloy portion 320 increases, and the
concentration of the metal group M increases as it approaches the
second dielectric ceramic layer 20b.
[0161] In the multilayer ceramic capacitor 1 of the present
preferred embodiment, in the plane of the multilayer body 10
including the central portion in the width (W) direction, the
length (L) direction, and the stacking (T) direction, the first
internal electrode layer 21 includes the first interspersed
internal electrodes 210 that are discontinuously interspersed in
the length (L) direction at the end in the length (L) direction
that is not connected to the second external electrode 52, the
second internal electrode layer 22 includes the second interspersed
internal electrodes 220 that are discontinuously interspersed in
the length (L) direction at the end in the length (L) direction
that is not connected to the first external electrode 51, and the
fourth alloy portion 340, which includes a metal element provided
in a greatest amount among the metal elements of the internal
electrode layer, and any one or more of metal elements among the
metal group M, is provided around each of the first interspersed
internal electrodes 210 and the second interspersed internal
electrodes 220.
[0162] When the first intersecting internal electrode 210 and the
second intersecting internal electrode 220 are respectively
connected to the first internal electrode layer 21 and the second
internal electrode layer 22 while extending in the width (W)
direction, if the electric field is concentrated in the connecting
portion, breakdown may occur which reduces reliability. However,
according to the multilayer ceramic capacitor 1 of the present
preferred embodiment, it is possible for the fourth alloy portion
340 provided around each of the first interspersed internal
electrodes 210 and the second interspersed internal electrodes 220
to reduce or prevent breakdown due to electric field concentration,
such that it is possible to improve the reliability.
[0163] In the multilayer ceramic capacitor 1 of the present
preferred embodiment, the third alloy portion 330, which includes a
metal element provided in a greatest amount among the metal
elements of the internal electrode layer, and any one or more of
metal elements among the above metal group M, is provided between
the third dielectric ceramic layer 41 and 42 and the first internal
electrode layer 21, and between the third dielectric ceramic layer
41 and 42 and the second internal electrode layer 22,
respectively.
[0164] Thus, the electric field concentration is reduced or
prevented at the portion in the vicinity of the interfaces with the
third dielectric ceramic layers 41 and 42 in the first internal
electrode layer 21 and the second internal electrode layer 22 by
the third alloy portion 330, thus making it possible to improve the
reliability.
[0165] In the multilayer ceramic capacitor 1 of the present
preferred embodiment, the first external electrode 51 and the
second external electrode 52 include Ni, and the fifth alloy
portion 350 in which any one or more of metal elements among the
metal group M is segregated in Ni is provided between the second
dielectric ceramic layer 20b, and the first external electrode 51
and the second external electrode 52.
[0166] Thus, even when the interval between the first internal
electrode layer 21 and the second external electrode 52, and the
interval between the second internal electrode layer 22 and the
first external electrode 51, i.e. the distance of the second
dielectric ceramic layer 20b in the length (L) direction is, for
example, as narrow as less than about 15 .mu.m, since the fifth
alloy portion 350 is present, which causes breakdown due to
electric field concentration to be less likely to occur between the
internal electrode layer and the external electrode, reliability is
improved.
Test Example 1
[0167] Next, Test Example 1 will be described which verifies the
advantageous effects of the first alloy portion 310, the second
alloy portion 320, and the third alloy portion 330 in the
multilayer ceramic capacitor 1 of the present preferred
embodiment.
Regarding TEM Analysis
[0168] In the manufacturing method for the multilayer ceramic
capacitor of the present preferred embodiment described above, the
multilayer body 10 obtained by firing the green chip 110 without
cofiring the first external electrode 51 and the second external
electrode 52 is polished from the first side surface 13 side and
the second side surface 14 side, to obtain a polished body leaving
the central portion in the width (W) direction as a test body, as
shown in FIG. 18. The type and the amount of metal (metal
concentration) of the metal elements included in the first alloy
portion 310 were analyzed as follows. As shown in FIG. 18, in the
central portion of the length (L) direction, an imaginary line OL1
orthogonal or substantially orthogonal to the length (L) direction
was assumed. Furthermore, the region in which the first dielectric
ceramic layer 20a in relation to the acquisition of the capacitance
of the polished body, and the first internal electrode layer 21 and
the second internal electrode layer 22 are stacked is equally
divided into three regions along the imaginary line OL1 in the
stacking direction. The three regions include an upper region E1, a
center region E2, and a lower region E3. The upper region E1, the
center region E2, and the lower region E3 are cut out from the
polished body, and each of the upper region E1, the center region
E2, and the lower region E3 is thinned by Ar ion milling or the
like, for example, to obtain three thin film samples from each
region.
[0169] The three thin film samples of the upper region E1, the
center region E2, and the lower region E3 of the test body obtained
as described above were subjected to TEM observation and elemental
mapping by EDX attached to the TEM. As a result, since there was no
significant difference between the upper region E1 and the lower
region E3, and the center region E2, the result obtained from the
center region E2 is regarded as the microstructure including the
dielectric ceramic layer and the internal electrode layer. As a
result, the type and the amount of metal (metal concentration) of
the metal elements included in the first alloy portion 310 are
known. In addition, the type and the amount of metal (metal
concentration) of the metal elements included in the second alloy
portion 320 can be analyzed by obtaining a thin film sample in the
same or substantially the same manner as described above in the
region of one end in the length (L) direction in which the second
alloy portion 320 exists. That is, in the polished body shown in
FIG. 18, an imaginary line OL2 orthogonal or substantially
orthogonal to the length (L) direction is assumed at one end in the
length (L) direction, to obtain thin film samples of three regions
including an upper region E4, a center region E5, and a lower
region E6 which are provided by dividing into three equal portions
along the imaginary line OL2 in the stacking direction.
Furthermore, the three thin film samples of the upper region E4,
the center region E5, and the lower region E6 were subjected to TEM
observation and element mapping by EDX attached to TEM, to examine
the type and the amount of metal (metal concentration) included in
the second alloy portion 320.
[0170] For the second alloy portion and the first alloy portion,
the concentration of Sn was examined by analysis with EDX mapping
image by a TEM observation image. The TEM measurement points were
measured at intervals of about 5 nm to about 10 nm. At the
interface between the internal electrode layer and the dielectric
ceramic layer, the region obtained three times or more of the
observed values than the other measurement points is regarded as
the alloy portion, and the average value is regarded as the metal
concentration of the alloy portion.
[0171] Eighteen multilayer ceramic capacitors were prepared for
each of Test Examples 1-1 to 1-5 shown in Table 1. In Test Example
1-2, in the multilayer ceramic capacitor of the present preferred
embodiment, the first internal electrode layer 21 and the second
internal electrode layer 22 were made of Ni, and the same amount of
Sn as an additive was added to the first dielectric ceramic layer
20a and the second dielectric ceramic layer 20b. In Test Examples
1-3 to 1-5, the amount of Sn added to the second dielectric ceramic
layer 20b was gradually larger than that in Test Example 1-2.
Furthermore, in Test Example 1-1, multilayer ceramic capacitors of
the same conditions as those in Test Examples 1-2 to 1-5 were used,
except that no Sn was added to the second dielectric ceramic layer
20b.
[0172] For the multilayer ceramic capacitors of Test Examples 1-1
to 1-5, the determination was made by measuring the resistance
value (k.OMEGA.) in a state in which a voltage of about 6.3 V was
applied in an environment with a room temperature of about
150.degree. C., to examine MTTF (mean failure time). MTTF was
determined when the resistance value became about 10 k.OMEGA. or
less, and if MTTF was about 15.3 hours (hr) or less, it was
evaluated as fail, if MTTF was up to about 30 hours beyond about
15.3 hours (hr), it is evaluated as good, and if MTTF was beyond
about 30 hours, it was evaluated as excellent. The results are
listed in Table 1. It should be noted that, when the coverage of
the internal electrode layer is less than about 80%, since the
capacitance is difficult to be measured, it was evaluated as
unmeasurable.
TABLE-US-00001 TABLE 1 Sn CONCEN- Sn CONCEN- TRATION TRATION OF
FIRST OF SECOND ALLOY ALLOY PORTION PORTION MTTF (at %) (at %) (hr)
EVALUATION TEST 1 0 15.3 FAIL EXAMPLE 1-1 TEST 1 1 21 GOOD EXAMPLE
1-2 TEST 1 1.1 21 GOOD EXAMPLE 1-3 TEST 1 1.3 23 GOOD EXAMPLE 1-4
TEST 1 1.4 35 EXCELLENT EXAMPLE 1-5
[0173] According to Table 1, it is confirmed that, since the second
alloy portion was provided, MTTF was beyond the prescribed time of
about 15.3 hours, and thus it was evaluated as good, and it is
further found that MTTF was better as the Sn concentration was
higher. On the other hand, in Test Example 1-1 in which the second
alloy portion including Sn was not provided, MTTF could not exceed
the prescribed time. Thus, it was confirmed that the second alloy
portion improved the reliability of the multilayer ceramic
capacitor.
[0174] Next, eighteen multilayer ceramic capacitors were prepared
for Test Examples 1-6 to 1-9 shown in Table 2, in addition to Test
Example 1-1. In Test Example 1-6, Sn as an additive was further
added to the third dielectric ceramic layer in the same amount as
that added to the first dielectric ceramic layer and the second
dielectric ceramic layer in Test Example 1-2. In Test Examples 1-7
to 1-9, the amount of Sn added to the third dielectric ceramic
layer was gradually larger than that in Test Examples 1-6. In Test
Example 1-1, Sn was not added to the third dielectric ceramic
layer.
[0175] For Test Examples 1-1 and 1-6 to 1-9, MTTF was determined in
the same manner as in Test Examples 1-1 to 1-5. The results are
shown in Table 2.
TABLE-US-00002 TABLE 2 Sn Sn Sn CONCENTRATION CONCENTRATION
CONCENTRATION OF FIRST ALLOY OF SECOND ALLOY OF THIRD ALLOY MTTF
PORTION (at %) PORTION (at %) PORTION (at %) (hr) EVALUATION TEST 1
0 0 15.3 FAIL EXAMPLE 1-1 TEST 1 1 1 22 GOOD EXAMPLE 1-6 TEST 1 1.1
1.2 25 GOOD EXAMPLE 1-7 TEST 1 1.3 1.3 27 GOOD EXAMPLE 1-8 TEST 1
1.4 1.4 41 EXCELLENT EXAMPLE 1-9
[0176] According to Table 2, it is confirmed that, since the third
alloy portion together with the second alloy portion was provided,
MTTF is beyond the prescribed time of about 15.3 hours, and thus it
was evaluated as good, and it is further found that MTTF was better
as the Sn concentration was higher. On the other hand, in Test
Example 1-1 in which the second alloy portion and the third alloy
portion including Sn were not provided, MTTF could not exceed the
prescribed time. Thus, it was confirmed that the second alloy
portion and the third alloy portion improved the reliability of the
multilayer ceramic capacitor.
(2) Average Particle Size of the Dielectric Particles Included Near
Intersection Region
[0177] FIG. 19 shows a plane including the length (L) direction and
the width (W) direction of the multilayer ceramic capacitor 1 of
the present preferred embodiment, and a plane including the second
dielectric ceramic layer 20b and the second internal electrode
layer 22. As shown in FIG. 19, both sides of the end closer to the
first end surface 15 in the multilayer ceramic capacitor 1 in the
width (W) direction each include an intersection 400 of the
interface surrounded by the second dielectric ceramic layer 20b,
the second internal electrode layer 22, and the third dielectric
ceramic layers 41 and 42. This intersection 400 is an intersection
of the interface 2220b between the second dielectric ceramic layer
20b and the second internal electrode layer 22, and an inner
surface 401 in the width (W) direction in the third dielectric
ceramic layers 41 and 42. Furthermore, similarly to this, both
sides closer to the second end surface 16 in the width (W)
direction each include the intersection 400 of the interface
surrounded by the second dielectric ceramic layer 20b, the first
internal electrode layer 21, and the third dielectric ceramic
layers 41 and 42.
[0178] An inner region of a circle 400r having a radius of about 5
.mu.m, for example, around the intersection 400 is defined as a
second near intersection region 420. An inner region of the circle
400r having a radius of about 5 .mu.m around the intersection 400
is defined as a third near intersection region 430. The region
inside the circle 400r also includes the line of the circle 400r.
In the following description, the second near intersection region
420 close to the second dielectric ceramic layer 20b, and a third
near intersection region 430 close to the third dielectric ceramic
layers 41 and 42 may be collectively referred to as a near
intersection region 440. The inner region of the second near
intersection region 420 includes a portion of the second dielectric
ceramic layer 20b. The inner region of the third near intersection
region 430 includes a portion of the third dielectric ceramic
layers 41 and 42.
[0179] In the multilayer ceramic capacitor 1 of the present
preferred embodiment, (A) the average particle size of the
dielectric particles included in each near intersection region 440
is preferably smaller than the average particle size of the
dielectric particles included in the first dielectric ceramic layer
20a, the dielectric particles included in the second dielectric
ceramic layer 20b, and the dielectric particles included in the
third dielectric ceramic layers 41 and 42.
[0180] In addition, in the multilayer ceramic capacitor 1 of the
present preferred embodiment, (B) it is preferable for the ratio of
the average particle size of the dielectric particles included in
each near intersection region 440 smaller than the average particle
size of the dielectric particles included therein to be about 5% or
more smaller, for example.
[0181] It should be noted that the average particle size of the
dielectric particles included in the second dielectric ceramic
layer 20b in this case refers to an average particle size of the
dielectric particles included in the second dielectric ceramic
layer 20b in a portion other than the second near intersection
region 420, and the average particle size of the dielectric
particles included in the third dielectric ceramic layers 41 and 42
refers to an average particle size of the dielectric particles
included in the third dielectric ceramic layers 41 and 42 in a
portion other than the third near intersection region 430.
[0182] The multilayer ceramic capacitor 1 of the present preferred
embodiment having the above configuration (A) or (B) preferably
further has any of the following configurations of (C) to (I).
[0183] (C) The difference between the average particle size of the
dielectric particles included in the second dielectric ceramic
layer 20b and the average particle size of the dielectric particles
included in the third dielectric ceramic layers 41 and 42 is within
about 5%, for example; the average particle size of the dielectric
particles included in the first dielectric ceramic layer 20a is
larger than the average particle size of the dielectric particles
included in the second dielectric ceramic layer 20b and the average
particle size of the dielectric particles included in the third
dielectric ceramic layers 41 and 42; and the average particle size
of the dielectric particles included in the near intersection
region 440 is smaller than the average particle size of the
dielectric particles included in the second dielectric ceramic
layer 20b and the average particle size of the dielectric particles
included in the third dielectric ceramic layers 41 and 42.
[0184] (D) The difference between the average particle size of the
dielectric particles included in the first dielectric ceramic layer
20a and the average particle size of the dielectric particles
included in the second dielectric ceramic layer 20b is within about
5%, for example; the average particle size of the dielectric
particles included in the third dielectric ceramic layer 41 and 42
is smaller than the average particle size of the dielectric
particles included in the first dielectric ceramic layer 20a and
the average particle size of the dielectric particles included in
the second dielectric ceramic layer 20b; and the average particle
size of the dielectric particles included in the near intersection
region 440 is smaller than the average particle size of the
dielectric particles included in the third dielectric ceramic
layers 41 and 42.
[0185] (E) The difference between the average particle size of the
dielectric particles included in the first dielectric ceramic layer
20a and the average particle size of the dielectric particles
included in the third dielectric ceramic layer 41 and 42 is within
about 5%, for example; the average particle size of the dielectric
particles included in the second dielectric ceramic layer 20b
smaller than the average particle size of the dielectric particles
included in the first dielectric ceramic layer 20a and the average
particle size of the dielectric particles included in the third
dielectric ceramic layer 41 and 42; and the average particle size
of the dielectric particles included in the near intersection
region 440 is smaller than the average particle size of the
dielectric particles included in the second dielectric ceramic
layer 20b.
[0186] (F) The difference between the average particle size of the
dielectric particles included in the first dielectric ceramic layer
20a and the average particle size of the dielectric particles
included in the second dielectric ceramic layer 20b is within about
5%, for example; the difference between the average particle size
of the dielectric particles included in the first dielectric
ceramic layer 20a and the average particle size of the dielectric
particles included in the third dielectric ceramic layers 41 and 42
is within about 5%, for example; and the difference between the
average particle size of the dielectric particles included in the
second dielectric ceramic layer 20b and the average particle size
of the dielectric particles included in the third dielectric
ceramic layers 41 and 42 is within about 5%, for example, and the
average particle size of the dielectric particles included in the
near intersection region 440 is smaller than the average particle
size of the dielectric particles included in the first dielectric
ceramic layer 20a, the average particle size of the dielectric
particles included in the second dielectric ceramic layer 20b, and
the average particle size of the dielectric particles included in
the third dielectric ceramic layers 41 and 42.
[0187] (G) The average particle size of the dielectric particles
included in the first dielectric ceramic layer 20a is smaller than
the average particle size of the dielectric particles included in
the second dielectric ceramic layer 20b; the average particle size
of the dielectric particles included in the third dielectric
ceramic layer 41 and 42 is smaller than the average particle size
of the dielectric particles included in the first dielectric
ceramic layer 20a; and the average particle size of the dielectric
particles included in the near intersection region 440 is smaller
than the average particle size of the dielectric particles included
in the third dielectric ceramic layers 41 and 42.
[0188] (H) The average particle size of the dielectric particles
included in the first dielectric ceramic layer 20a is smaller than
the average particle size of the dielectric particles included in
the third dielectric ceramic layer 41 and 42; the average particle
size of the dielectric particles included in the second dielectric
ceramic layer 20b is smaller than the average particle size of the
dielectric particles included in the first dielectric ceramic layer
20a; and the average particle size of the dielectric particles
included in the near intersection region 440 is smaller than the
average particle size of the dielectric particles included in the
second dielectric ceramic layer 20b.
[0189] (I) The average particle size of the dielectric particles
included in the near intersection region 440 is smaller than the
average particle size of the dielectric particles included in the
first dielectric ceramic layer 20a; and the average particle size
of the dielectric particles included in the third dielectric
ceramic layers 41 and 42 or the average particle size of the
dielectric particles included in the second dielectric ceramic
layer 20b is smaller than the average particle size of the
dielectric particles included in the near intersection region
440.
[0190] It is possible to control the average particle size of the
dielectric particles included in the first dielectric ceramic layer
20a, the second dielectric ceramic layer 20b, and the third
dielectric ceramic layer 41 and 42 by adjusting the amount of
sintering aid such as Si, Mn, etc., for example, included in the
dielectric ceramic slurry forming each dielectric ceramic layer,
and further adjusting the firing temperature.
[0191] As described above, in the multilayer ceramic capacitor 1 of
the present preferred embodiment, the average particle size of the
dielectric particles included in the near intersection region 440
is smaller than the average particle size of the dielectric
particles included in the first dielectric ceramic layer 20a and
the dielectric particles included in the second dielectric ceramic
layer 20b around the near intersection region 440, and the average
particle size of the dielectric particles included in the third
dielectric ceramic layer 41 and 42.
[0192] The electric field is likely to be concentrated in the near
intersection region 440, and the occurrence of the electric field
concentration may degrade the reliability of a multilayer ceramic
capacitor. However, in the multilayer ceramic capacitor 1 of the
present preferred embodiment, the average particle size of the
dielectric particles included in the near intersection region 440
is smaller than the average particle size of the dielectric
particles included in each of the first dielectric ceramic layer
20a, the second dielectric ceramic layer 20b, and the third
dielectric ceramic layers 41 and 42 therearound. Thus, since the
average particle size is small, electric field concentration is
reduced or prevented by the presence of many grain boundaries. As a
result, it is possible to improve the reliability of a multilayer
ceramic capacitor.
Test Example 2
[0193] Next, Test Example 2 will be described which verifies that
it is superior in that the multilayer ceramic capacitor 1 of the
present preferred embodiment having the average particle size of
the dielectric particles included in the near intersection region
440 which is smaller than the average particle size of the
dielectric particles included in each of the first dielectric
ceramic layer 20a and the third dielectric ceramic layers 41 and 42
therearound.
[0194] The average particle sizes of the dielectric particles
included in each of the first dielectric ceramic layer, the second
dielectric ceramic layer, and the third dielectric ceramic layer
are measured as follows.
Average Particle Size of the Dielectric Particles Included in the
First Dielectric Ceramic Layer
[0195] In the non-limiting example of a manufacturing method for
the multilayer ceramic capacitor of the present preferred
embodiment described above, the multilayer body 10 obtained by
firing the green chip 110 without cofiring the first external
electrode 51 and the second external electrode 52 is polished from
the first end surface 15 side or the second end surface 16 side, to
obtain a polished body leaving the central portion in the length
(L) direction as a test body, as shown in FIG. 20. As shown in FIG.
20, in the central portion of the width (W) direction, an imaginary
line OS1 orthogonal or substantially orthogonal to the width (W)
direction was assumed. Furthermore, the region in which the first
dielectric ceramic layer 20a in relation to the acquisition of the
capacitance of the polished body, and the first internal electrode
layer 21 and the second internal electrode layer 22 are stacked was
equally divided into three regions along the imaginary line OS1 in
the stacking direction. The three regions include an upper region
F1, a center region F2, and a lower region F3. For each of the
regions F1, F2, and F3, the first dielectric ceramic layer 20a was
imaged with a field size of about 4.3 .mu.m.times.about 3.2 .mu.m,
and for each of the regions F1, F2, and F3, the area was measured
by image processing for 20 pieces of dielectric particles. Then,
the equivalent circle diameter was calculated from the measured
area and averaged to obtain the average particle size. The average
particle size was measured in each of the upper region F1, the
center region F2, and the lower region F3, and no significant
difference was found in the measured values. Therefore, the average
particle size of the center region F2 is regarded as the average
particle size of the first dielectric ceramic layer.
Average Particle Size of the Dielectric Particles Included in the
Third Dielectric Ceramic Layer
[0196] In the test body shown in FIG. 20, an imaginary line is
assumed which connects the ends of the plurality of first internal
electrode layers 21 and the plurality of second internal electrode
layers 22 closer to the first side surface 13 or the second side
surface 14 in the stacking (T) direction. FIG. 20 shows an
imaginary line OS3 which connects the ends of the plurality of
first internal electrode layers 21 and the plurality of second
internal electrode layers 22 close to the second side surface 14 in
the stacking (T) direction. As shown in FIG. 21, the third
dielectric ceramic layer 42 was imaged from the virtual line OS3 at
a field size about 4.3 .mu.m.times.about 3.2 .mu.m in the range of
about 5 .mu.m on the third dielectric ceramic layer 42 side, and
for each of the regions F1, F2, and F3, the area was measured by
image processing for 20 pieces of dielectric particles. The
reference numeral 42F in FIG. 21 indicates an imaging region. Then,
the equivalent circle diameter was calculated from the measured
area and averaged to obtain the average particle size. The average
particle size was measured in each of the upper region F1, the
center region F2, and the lower region F3, and no significant
difference was found in the measured values. Therefore, the average
particle size of the center region F2 is regarded as the average
particle size of the third dielectric ceramic layer.
Average Particle Size of the Dielectric Particles Included in the
Second Dielectric Ceramic Layer
[0197] The multilayer body 10 is polished from the first end
surface 15 side or the second end surface 16 side, until just
before at least one internal electrode layer is exposed. For
example, as shown in FIG. 22, polishing is performed from the
second end surface 16 side to a surface J immediately before the
second internal electrode layer 22 appears. As shown in FIG. 23, in
the central portion in the width (W) direction, an imaginary line
OS2 perpendicular or substantially perpendicular to the width (W)
direction was assumed. Then, along the imaginary line OS2, the
second dielectric ceramic layer 20b was divided into three equal
portions of an upper region G1, a center region G2, and a lower
region G3 in the stacking direction. For each of the regions G1,
G2, and G3, the second dielectric ceramic layer was imaged with a
field size of about 4.3 .mu.m.times.about 3.2 .mu.m, and for each
of the regions G1, G2 and G3, the area was measured by image
processing for 20 pieces of dielectric particles. Then, the
equivalent circle diameter was calculated from the measured area
and averaged to obtain the average particle size. The average
particle size was measured in each of the upper region G1, the
center region G2, and the lower region G3, and no significant
difference was found in the measured values. Therefore, the average
particle size of the center region G2 is regarded as the average
particle size of the second dielectric ceramic layer.
Average Particle Size of Dielectric Particles Included in the Near
Intersection Region
[0198] In the test body shown in FIG. 23, an imaginary line OS4 is
assumed which connects the ends of the plurality of first internal
electrode layers 21 and the plurality of second internal electrode
layers 22 closer to the second side surface 14 in the stacking (T)
direction. Then, along the imaginary line OS4, the region on both
sides in the width (W) direction of the imaginary line OS4
including the near intersection region 440 was divided into three
equal regions in the stacking direction. The three equal region
includes an upper region H1, a center region H2, and a lower region
H3. As shown in FIG. 24, the second dielectric ceramic layer 20b
and the third dielectric ceramic layer 42 were imaged in a field
size of about 4.3 .mu.m.times.about 3.2 .mu.m in the range of 5
.mu.m in the width (W) direction on both sides of the virtual line
OS4, and for each of the regions F1, F2, and F3, the area was
measured by image processing for 20 pieces of dielectric particles.
Reference numeral 42H in FIG. 24 indicates an imaging region. Then,
the equivalent circle diameter was calculated from the measured
area and averaged to obtain the average particle size. The average
particle size was measured in each of the upper region H1, the
center region H2, and the lower region H3, and no significant
difference was found in the measured values. Therefore, the average
particle size of the center region H2 is regarded as the average
particle size of the near intersection region 440.
[0199] Test Examples 2-1 to 2-24 shown in Table 3 were prepared as
the multilayer ceramic capacitors corresponding to (C) to (I)
described above. Furthermore, for Test Examples 2-25 to 2-27, the
average particle size of the dielectric particles included in the
near intersection region 440 was larger than the average particle
size of the dielectric particles included in the first dielectric
ceramic layer 20a, the average particle size of the dielectric
particles included in the second dielectric ceramic layer 20b, and
the average particle size of the dielectric particles included in
the third dielectric ceramic layers 41 and 42. The average particle
sizes of Test Examples 2-1 to 2-27 were examined by the measurement
method described above.
[0200] In Table 3, "first" in the item of comparison of the average
particle size refers to the average particle size of the dielectric
particles included in the first dielectric ceramic layer; "second"
refers to the average particle size of the dielectric particles
included in the second dielectric ceramic layer; "third" refers to
the average particle size of the dielectric particles included in
the third dielectric ceramic layer; and "intersection" refers to
the average particle size of the dielectric particles included in
the near intersection region.
[0201] On the other hand, for the multilayer ceramic capacitors of
the Test Examples 2-25 to 2-27, the determination was performed by
measuring the resistance value (k.OMEGA.) in a state in which
voltage of about 6.3 V was applied in an environment with a room
temperature of about 150.degree. C., to examine MTTF (mean failure
time). MTTF was determined when the resistance value became about
10 k.OMEGA. or less, and if MTTF was about 15.3 hours (hr) or less,
it was evaluated as fail, if MTTF was up to about 30 hours beyond
about 15.3 hours (hr), it is evaluated as good, and if MTTF was
beyond about 30 hours, it was evaluated as excellent. The results
are listed in Table 3. It should be noted that, when the coverage
of the internal electrode layer is less than about 80%, since the
capacitance is difficult to be measured, it was evaluated as
unmeasurable.
TABLE-US-00003 TABLE 3 AVERAGE AVERAGE AVERAGE PARTICLE PARTICLE
PARTICLE SIZE OF SIZE OF SIZE OF FIRST SECOND THIRD DIELECTRIC
DIELECTRIC DIELECTRIC OMPARISON OF AVERAGE TEST CERAMIC CERAMIC
CERAMIC INTER MTTF PARTICLE DIAMETER EXAMPLE LAYER (.mu.m) LAYER
(.mu.m) LAYER (.mu.m) SECTION (hr) EVALUATION (C) FIRST > SECOND
= TEST 0.42 0.32 0.33 0.15 32.1 EXCELLENT THIRD > INTERSECTION
EXAMPLE2-1 (C) FIRST > SECOND = TEST 0.65 0.33 0.32 0.13 33.9
EXCELLENT THIRD > INTERSECTION EXAMPLE2-2 (C) FIRST > SECOND
= TEST 0.71 0.31 0.33 0.14 33.1 EXCELLENT THIRD > INTERSECTION
EXAMPLE2-3 (D) FIRST = SECOND > TEST 0.42 0.41 0.32 0.12 34.1
EXCELLENT THIRD > INTERSECTION EXAMPLE2-4 (D) FIRST = SECOND
> TEST 0.65 0.66 0.33 0.11 35.2 EXCELLENT THIRD >
INTERSECTION EXAMPLE2-5 (D) FIRST = SECOND > TEST 0.71 0.72 0.35
0.13 33.8 EXCELLENT THIRD > INTERSECTION EXAMPLE2-6 (E) FIRST =
THIRD > TEST 0.42 0.32 0.41 0.15 32.1 EXCELLENT SECOND >
INTERSECTION EXAMPLE2-7 (E) FIRST = THIRD > TEST 0.65 0.33 0.66
0.11 35.1 EXCELLENT SECOND > INTERSECTION EXAMPLE2-8 (E) FIRST =
THIRD > TEST 0.71 0.35 0.72 0.14 33.1 EXCELLENT SECOND >
INTERSECTION EXAMPLE2-9 (F) FIRST = SECOND = TEST 0.42 0.43 0.42
0.11 35.6 EXCELLENT THIRD > INTERSECTION EXAMPLE2-10 (F) FIRST =
SECOND = TEST 0.65 0.66 0.64 0.13 22.9 EXCELLENT THIRD >
INTERSECTION EXAMPLE2-11 (F) FIRST = SECOND = TEST 0.71 0.72 0.71
0.12 34.0 EXCELLENT THIRD > INTERSECTION EXAMPLE2-12 (G) SECOND
> FIRST > TEST 0.42 0.51 0.35 0.15 32.1 EXCELLENT THIRD >
INTERSECTION EXAMPLE2-13 (G) SECOND > FIRST > TEST 0.65 0.73
0.57 0.16 31.6 EXCELLENT THIRD > INTERSECTION EXAMPLE2-14 (G)
SECOND > FIRST > TEST 0.71 0.85 0.66 0.13 33.7 EXCELLENT
THIRD > INTERSECTION EXAMPLE2-15 (E) THIRD = FIRST > TEST
0.42 0.32 0.43 0.14 33.1 EXCELLENT SECOND > INTERSECTION
EXAMPLE2-16 (E) THIRD = FIRST > TEST 0.65 0.56 0.66 0.12 34.2
EXCELLENT SECOND > INTERSECTION EXAMPLE2-17 (E) THIRD = FIRST
> TEST 0.71 0.65 0.72 0.13 33.8 EXCELLENT SECOND >
INTERSECTION EXAMPLE2-18 (H) THIRD > FIRST > TEST 0.52 0.42
0.33 0.16 31.6 EXCELLENT SECOND > INTERSECTION EXAMPLE2-19 (H)
THIRD > FIRST > TEST 0.72 0.66 0.62 0.12 34.3 EXCELLENT
SECOND > INTERSECTION EXAMPLE2-20 (H) THIRD > FIRST > TEST
0.86 0.7 0.75 0.14 33.1 EXCELLENT SECOND > INTERSECTION
EXAMPLE2-21 (I) FIRST > TEST 0.41 0.31 0.25 0.24 27.6 GOOD
INTERSECTION > SECOND EXAMPLE2-22 or THIRD (I) FIRST > TEST
0.65 0.45 0.32 0.33 14.6 FAIL INTERSECTION > SECOND EXAMPLE2-23
or THIRD (I) FIRST > TEST 0.73 0.55 0.44 0.43 13.1 FAIL
INTERSECTION > SECOND EXAMPLE2-24 or THIRD INTERSECTION >
THIRD = TEST 0.42 0.41 0.42 0.91 9.1 FAIL FIRST = SECOND
EXAMPLE2-25 INTERSECTION > THIRD = TEST 0.52 0.51 0.51 0.9 8.9
FAIL FIRST = SECOND EXAMPLE2-26 INTERSECTION > THIRD = TEST 0.71
0.72 0.71 0.9 8.7 FAIL FIRST = SECOND EXAMPLE2-27
[0202] According to Table 3, it is confirmed that, when the average
particle size of the dielectric particles included in the near
intersection region was smaller than the average particle size of
the dielectric particles included in each of the first dielectric
ceramic layer, the second dielectric ceramic layer, and the third
dielectric ceramic layer, MTTF was increased, which improved the
reliability of the multilayer ceramic capacitor.
(3) Method for Manufacturing with the Addition of a Step of
Removing the Side Surface of the Multilayer Body
[0203] In a non-limiting example of a method for manufacturing the
multilayer ceramic capacitor 1 of the present preferred embodiment
described above, in order to obtain the green chip 110 which is the
unfired multilayer body 10, the method includes the steps of:
printing the unfired first internal electrode layer 121 and second
internal electrode layer 122 on the unfired first dielectric
ceramic layer 120a; forming the unfired second dielectric ceramic
layer 120b in a region other than the region of the first
dielectric ceramic layer 120a where the first internal electrode
layer 121 and the second internal electrode layer 122 are printed;
stacking the plurality of first dielectric ceramic layer 120a to
form the green chip 110; exposing, by cutting the mother block 104,
the first internal electrode layer 121 and the second internal
electrode layer 122, the first dielectric ceramic layer 120a, and
the second dielectric ceramic layer 120b from the first side
surface 113 and the second side surface 114 of the individual green
chips 110; and bonding the unfired third dielectric ceramic layer
(the side margin portions 41 and 42) to the first side surface 113
and the second side surface 114 of the individual green chips 110.
Here, the green chip 110 is an example of a multilayer body. The
first dielectric ceramic layer 120a is an example of a dielectric
layer. The first internal electrode layer 121 and the second
internal electrode layer 122 are examples of internal electrode
patterns. The second dielectric ceramic layer 120b is an example of
a dielectric pattern. The first side surface 113 and the second
side surface 114 are examples of side surfaces. The side margin
portions 41 and 42 which are the unfired third dielectric ceramic
layer are examples of a dielectric gap layer.
[0204] In this manufacturing method, it is possible to add a step
of removing a certain thickness of the first side surface 113 and
the second side surface 114 after the step of exposing, by cutting
the mother block 104, the first internal electrode layer 121 and
the second internal electrode layer 122, the first dielectric
ceramic layer 120a, and the second dielectric ceramic layer 120b
from the first side surface 113 and the second side surface 114 of
the green chips 110; and before the step of bonding the third
dielectric ceramic layer to the first side surface 113 and the
second side surface 114 of the green chips 110. Thus, the side
surfaces of the first dielectric ceramic layer 120a, the second
dielectric ceramic layer 120b, and the first internal electrode
layer 121 and the second internal electrode layer 122 exposed on
the first side surface 113 and the second side surface 114 are
removed.
[0205] FIG. 25 shows a state in which the first side surface 113
and the second side surface 114 of the green chip 110 are flattened
by removing a certain thickness (for example, about 1 .mu.m or
less) therefrom. In FIG. 25, the diagram on the left side shows
before the step of removing, and the diagram on the right side
shows after the step of removing. When obtaining the plurality of
green chips 110 by cutting the mother block 104, the side surfaces
of the first side surface 113 and second side surface 114 of the
green chip 110 may be slightly bent downward, and thus, plastically
deformed due to the stress applied to the lower side in the drawing
which is a cutting direction, as shown in FIG. 25. In addition, the
cut surface may not be sufficiently smooth, or foreign matter may
exist in the cut surface. For this reason, the thickness to the
extent that the deformed portion is eliminated is removed. Although
the method for removing the first side surface 113 and the second
side surface 114 is not limited, for example, polishing by an
appropriate polishing method, for example, is preferably used.
[0206] As shown in FIG. 26, the first side surface 113 and the
second side surface 114 after the step of removing are formed to be
smooth surfaces from which foreign matter is removed. The third
dielectric ceramic layer (the side margin portions 41 and 42) is
bonded to the first side surface 113 and the second side surface
114 after the step of removing.
[0207] In preferred embodiments of the present invention, each of
the second dielectric ceramic layer 20b, and the first internal
electrode layer 21 and the second internal electrode layer 22 may
include a resin. The resin can be included in the material by being
added at the time of manufacturing. That is, the resin is included
in the dielectric paste in the second dielectric ceramic layer 20b,
and the resin is included in the conductive paste in the first
internal electrode layer 21 and the second internal electrode layer
22.
[0208] The resin included in the dielectric paste and the
conductive paste is added for the purpose of defining and
functioning as a binder, improving viscosity of the material, and
the like. Examples of such resins include polyvinyl acetal resins,
such as polyvinyl butyral and polyvinyl acetoacetal, polyvinyl
alcohol-based resins, such as polyvinyl alcohol, cellulosic resins
such as methylcellulose, ethylcellulose, and cellulose phthalate
acetate, (meth)acrylic resins, such as (meth)acrylic acid esters,
imide resins such as polyamideimide and polyimide, ethylene-based
resins, such as polyethylene oxide, nitrile resins, such as
polyacrylonitrile and polymetallilonitrile, urethane resins, such
as polyurethane, vinyl resins, such as polyethylene, polypropylene,
and vinyl acetate, and rubber-based resins, such as
styrene-butadiene rubber. However, the present invention is not
limited thereto.
[0209] As the content of the resin, the content included in the
second dielectric ceramic layer 20b and the content included in the
first dielectric ceramic layer 20a are preferably different from
one another. The resin contents of the first dielectric ceramic
layer 20a and the second dielectric ceramic layer 20b are
preferably about 30 wt % or more and about 50 wt % or less, for
example. The resin contents of the first dielectric ceramic layer
and the second dielectric ceramic layer 20b are preferably
different from each other in this range.
[0210] In a non-limiting example of a method for manufacturing a
multilayer ceramic capacitor according to a preferred embodiment of
the present invention, the thickness of the first dielectric
ceramic layer 120a is preferably about 0.4 .mu.m or more and about
0.8 .mu.m or less, for example. In a non-limiting example of a
method for manufacturing a multilayer ceramic capacitor according
to a preferred embodiment of the present invention, the thickness
of the first internal electrode layer 121 and the second internal
electrode layer 122 is preferably about 0.4 .mu.m or more and about
0.8 .mu.m or less, for example.
[0211] Furthermore, in forming the green chip 110, a portion of the
second internal electrode layer 122 may overlap with a portion of
the first internal electrode layer 121 and a portion of the second
internal electrode layer 122. More specifically, the ends of the
second dielectric ceramic layer 120b, and the first internal
electrode layer 121 and the second internal electrode layer 122
adjacent to each other in the length (L) direction may be
superimposed on each other. For example, as shown in FIG. 27, in
the length (L) direction, the end of the second dielectric ceramic
layer 120b may be superimposed on the end of the first internal
electrode layer 121. Similarly to this, an end of the second
dielectric ceramic layer 120b may be superimposed on an end of the
second internal electrode layer 122. In the configuration in which
the ends of the length (L) direction are superimposed on each
other, the end of the first internal electrode layer 121 and the
end of the second dielectric ceramic layer 120b may be superimposed
on the end of the second dielectric ceramic layer 120b.
[0212] A non-limiting example of a method for manufacturing a
multilayer ceramic capacitor according to a preferred embodiment of
the present invention includes removing a certain thickness of the
first side surface 113 and the second side surface 114 of the green
chip 110 which is the unfired multilayer body 10, following by
pasting the unfired third dielectric ceramic layer to the first
side surface 113 and the second side surface 114. Thus, it is
possible to form the unfired third dielectric ceramic layer with
respect to the first side surface 113 and the second side surface
114 in a smooth and clean state.
[0213] In the non-limiting example of a method for manufacturing a
multilayer ceramic capacitor according to a preferred embodiment of
the present invention, by removing the first side surface 113 and
the second side surface 114 by polishing, it is possible to remove
the first side surface 113 and the second side surface 114 easily
and accurately by a removal amount with a predetermined
thickness.
[0214] In a non-limiting example of a method for manufacturing a
multilayer ceramic capacitor according to a preferred embodiment of
the present invention, the second dielectric ceramic layer 120b
includes a resin, and the amount of the resin is preferably larger
than the amount of the resin included in the first internal
electrode layer 121 and the second internal electrode layer 122.
Thus, the viscosity of the second dielectric ceramic layer 120b is
relatively increased, and it is possible to reduce or prevent the
occurrence of defects, such as cracks and chips, in the cut surface
of the second dielectric ceramic layer 20b when cutting the mother
block 104.
[0215] In addition, in a non-limiting example of a method for
manufacturing a multilayer ceramic capacitor according to a
preferred embodiment of the present invention, the thickness of the
first dielectric ceramic layer 120a is preferably about 0.4 .mu.m
or more and about 0.8 .mu.m or less, for example, and the thickness
of the first internal electrode layer 121 and the second internal
electrode layer 122 is preferably about 0.4 .mu.m or more and about
0.8 .mu.m or less, for example. By the unfired dielectric layer and
the internal electrode layer having such a thickness, it is
possible to allow the first dielectric ceramic layer 20a, the first
internal electrode layer 21, and the second internal electrode
layer 22 after firing to be formed to have a suitable
thickness.
[0216] Moreover, a non-limiting example of a method for
manufacturing a multilayer ceramic capacitor according to a
preferred embodiment of the present invention, a portion of the
second internal electrode layer 122 may overlap the first internal
electrode layer 121 and the second internal electrode layer 122.
Thus, after firing, it is possible to form the second dielectric
ceramic layer 20b with a sufficient thickness without any gap.
(4) Defect Portion in the Second Dielectric Ceramic Layer
[0217] In the multilayer ceramic capacitor 1 of the present
preferred embodiment, as shown in FIGS. 28 and 29, there is a
defect portion 520 provided by being partially missing in the
second dielectric ceramic layer 20b between at least one second
dielectric ceramic layer 20b and one third dielectric ceramic layer
42. Furthermore, similarly to this, there is a defect portion 520
provided by being partially missing in the second dielectric
ceramic layer 20b between the at least one second dielectric
ceramic layer 20b and the other third dielectric ceramic layer
41.
[0218] In the region where the second dielectric ceramic layer 20b
is disposed, i.e. in at least one of the region between the end of
the first internal electrode layer 21 which is not connected to the
second external electrode 52 and the second external electrode 52
and the region between the end of the second internal electrode
layer 22 which is not connected to the first external electrode 51
and the first external electrode 51 in the length (L) direction of
the multilayer body 10, the defect portion 520 is included between
the first dielectric ceramic layers 20a at the position in the
stacking (T) direction on the plane including the stacking (T)
direction and the width (W) direction, and is included between the
second dielectric ceramic layer 20b and the third dielectric
ceramic layer 41 or 42 at the position in the width (W)
direction.
[0219] When fabricating the green chip 110 which is the unfired
multilayer body 10, the side surface of the unfired second
dielectric ceramic layer 120b is subjected to processing followed
by firing, to obtain the multilayer body 10 having the defect
portion 520 on the side surface of the second dielectric ceramic
layer 20b. Any method can be used as the processing method for
obtaining the defective portion 520, and for example, the defect
portion 520 can be formed by drilling with a suitable tool or the
like.
[0220] Furthermore, in "Method for manufacturing with the addition
of a step of removing the side surface of the multilayer body"
described above, when the first side surface 113 or the second side
surface 114 of the unfired green chip 110 is removed by polishing
or the like, a portion of the side surface of the second dielectric
ceramic layer 20b may be missing, and a fine hole may be formed. If
such a hole occurs, the hole may be a defect portion 520. The
defect portion 520 may not be formed on the side surface of all the
second internal electrode layer 22, and it suffices if one or more
of the defect portions 520 is formed on each of the first side
surface 13 side and the second side surface 14 side at both ends of
the length (L) direction.
[0221] Furthermore, as shown in FIGS. 28 and 29, a segregation 530
of Si may be disposed in the defect portion 520. The segregation
530 of Si is a segregation of Si added to the second dielectric
ceramic layer 20b as an additive.
[0222] The size of the segregation 530 of Si when viewed in the
diameter of the equivalent circle diameter is preferably, for
example, larger than about 1/3 of the thickness of the second
dielectric ceramic layer 20b. Furthermore, the size may preferably
be about 100 nm or more and about 600 nm or less, for example.
[0223] The defect portion 520 is preferably disposed close to the
first internal electrode layer 21 or the second internal electrode
layer 22. In FIG. 29, the defect portion 520 is disposed close to
the end of the second internal electrode layer 22 in the length (L)
direction. Similarly to this, the defect portion 520 is preferably
disposed close to the end of the first internal electrode layer 21
in the length (L) direction.
[0224] The dimension of the segregation 530 of Si is preferably
about 0.1% or more and about 5% or less, for example, of the
dimensions of the third dielectric ceramic layers 41 and 42 in the
width (W) direction.
[0225] In the region where the second dielectric ceramic layer 20b
is disposed, i.e. in at least one region in the length (L)
direction of the multilayer body 10 between the end of the first
internal electrode layer 21 which is not connected to the second
external electrode 52 and the second external electrode 52 and the
region between the end of the second internal electrode layer 22
which is not connected to the first external electrode 51 and the
first external electrode 51, the multilayer ceramic capacitor 1
includes the defect portion 520 which is between the first
dielectric ceramic layers 20a at the position in the stacking (T)
direction on the plane including the stacking (T) direction and the
width (W) direction, and is between the second dielectric ceramic
layer 20b and the third dielectric ceramic layer 41 or 42 at the
position in the width (W) direction.
[0226] Thus, it is possible to alleviate the stress generated in
the second dielectric ceramic layer 20b at the time of firing by
the defect portion 520. As a result, it is possible to reduce or
prevent cracking or chipping from occurring in the second
dielectric ceramic layer 20b.
[0227] In the multilayer ceramic capacitor 1, the segregation 530
of Si may be disposed at the defect portion 520. If the segregation
530 exists in the defect portion 520, entry of moisture is reduced
or prevented by the segregation 530. Due to the segregation 530
being present in the defect portion 520, the humidity resistance of
the multilayer ceramic capacitor 1 is improved. The segregation 530
may be present in all of the defect portions 520 or may be present
in a portion of the defect portion 520. With the defect portion 520
in which the segregation 530 is present, it is possible to reduce
or prevent cracking or chipping from occurring in the second
dielectric ceramic layer 20b, and the humidity resistance of the
multilayer ceramic capacitor 1 can be improved.
[0228] In the multilayer ceramic capacitor 1 of the present
preferred embodiment, the segregation 530 of Si is preferably about
1/3 or more (or less than about 1/3) of the thickness of the second
dielectric ceramic layer 20b.
[0229] In the multilayer ceramic capacitor 1, the defect portion
520 is disposed close to the first internal electrode layer 21 and
the second internal electrode layer 22. The region close to the
first internal electrode layer 21 and the second internal electrode
layer 22 receives a relatively large stress generated at the time
of firing. However, the stress is alleviated by the defect portion
520, and as a result of which the occurrence of cracking or
chipping can be effectively reduced or prevented.
[0230] In the multilayer ceramic capacitor 1, in the width
direction, the dimension of the segregation 530 of Si is preferably
about 0.1% or more and about 5% or less, for example, of the
dimensions of the third dielectric ceramic layers 41 and 42. When
the segregation 530 of Si is present in the defect portion 520, it
is possible to effectively reduce or prevent the occurrence of
cracking and chipping, and it is also possible to improve the
humidity resistance of the multilayer ceramic capacitor 1.
(5) Segregation at the End of the Internal Electrode Layer Side of
the Second Dielectric Ceramic Layer
[0231] As shown in FIG. 30, in the multilayer ceramic capacitor 1
of the present preferred embodiment, a first segregation 610 may be
present at the end in the length (L) direction of the first
internal electrode layer 21 which is not connected to the second
external electrode 52. In addition, the first segregation 610 may
be present at the end in the length (L) direction of the second
internal electrode layer 22 which is not connected to the first
external electrode 51.
[0232] As shown in FIG. 31, the first segregation 610 is generated
due to a metal element 610a originating from the second dielectric
ceramic layer 20b being segregated in a layered structure. Examples
of the metal element 610a include at least one among Mg, Mn, and
Si. The segregation 610 due to the metal element 610a occurs when
the metal element included in the second dielectric ceramic layer
20b migrates to the first internal electrode layer 21 and the
second internal electrode layer 22 during firing of the second
dielectric ceramic layer 20b.
[0233] On the other hand, as shown in FIG. 32, a second segregation
620 may be present at the end of the first internal electrode layer
21 in the width (W) direction. Furthermore, the second segregation
620 may be present at the end of the second internal electrode
layer 22 in the width (W) direction.
[0234] The second segregation 620 is generated due to a metal
element 620a originating from the third dielectric ceramic layers
41 and 42 in contact with the first internal electrode layer 21 and
the second internal electrode layer 22 being segregated in a
layered form. Similarly to the first segregation 610, examples of
the metal element 620a include at least one among Mg, Mn, and Si.
The segregation 620 due to the metal element 620a is generated is
due to the metal element included in the third dielectric ceramic
layers 41 and 42 migrating to the first internal electrode layer 21
and the second internal electrode layer 22 during firing of the
third dielectric ceramic layers 41 and 42.
[0235] In the multilayer ceramic capacitor 1, the first segregation
610 segregated in the first internal electrode layer 21, the first
segregation 610 segregated in the second internal electrode layer
22, the second segregation 620 segregated in the first internal
electrode layer 21, and the second segregation 620 segregated in
the second internal electrode layer 22 are preferably different
from one another in the metal element included in at least one set
of segregations therein.
[0236] When the first dielectric ceramic layer 20a includes
BaTiO.sub.3 as a main component, the content of the metal element
included in the first segregation 610 with respect to the first
internal electrode layer 21 and the second internal electrode layer
22 is preferably, for example, about 0.3 mol % or more with respect
to 100 moles of Ti. Similarly to this, the content of the metal
element included in the second segregation 620 with respect to the
first internal electrode layer 21 and the second internal electrode
layer 22 is preferably, for example, about 0.3 mol % or more with
respect to 100 moles of Ti.
[0237] In a preferred embodiment of the present invention, the
length along the length (L) direction of the region in which the
first segregation 610 is present in the first internal electrode
layer 21 is preferably about 0.1 .mu.m or more, for example.
Furthermore, the length along the length (L) direction of the
region in which the first segregation 610 is present in the second
internal electrode layer 22 is preferably about 0.1 .mu.m or more,
for example. Furthermore, the length along the width (W) direction
of the region in which the second segregation 620 is present in the
first internal electrode layer 21 is preferably about 0.1 .mu.m or
more, for example. Furthermore, the length along the width (W)
direction in the region in which the second segregation 620 is
present in the second internal electrode layer 22 is preferably
about 0.1 .mu.m or more, for example. By having these lengths,
electric field concentration can be reduced or prevented, and thus
it is possible to reliably obtain the advantageous effect of
improving the reliability.
[0238] With regard to the length of the first segregation 610 and
the second segregation 620, when a length becomes below the above
length, it is difficult to reduce the electric field concentration.
Furthermore, in the first segregation 610, if it exceeds about 0.5%
of the length (L) direction, or in the second segregation 620, if
it exceeds about 1.0% of the width (W) direction, the metal element
to be segregated (at least one of Mg, Mn, and Si, for example)
becomes excessive, and the function of storing the charge of the
internal electrode layer is degraded.
[0239] The length of the first segregation 610 in the length (L)
direction can be controlled by adjusting the content of the metal
element 610a included in the second dielectric ceramic layer 20b
and migrating to the first internal electrode layer 21 and the
second internal electrode layer 22 to be segregated. Furthermore,
the length of the second segregation 620 in the width (W) direction
can be controlled by adjusting the content of the metal element
620a included in the third dielectric ceramic layers 41 and 42, and
migrating to the first internal electrode layer 21 and the second
internal electrode layer 22 to be segregated.
[0240] In the multilayer ceramic capacitor 1, the first segregation
610 by at least one metal element selected from the group
consisting of Mg, Mn, and Si, for example, is present in each of
the end in the length (L) direction which is not connected to the
second external electrode 52 in the first internal electrode layer
21, and the end in the length (L) direction which is not connected
to the first external electrode 51 in the second internal electrode
layer 22.
[0241] The electric field is likely to be concentrated at the end
in the length (L) direction of each of the first internal electrode
layer 21 and the second internal electrode layer 22 in contact with
the second dielectric ceramic layer 20b, and when the electric
field concentration occurs, the reliability of a multilayer ceramic
capacitor may be reduced. However, in the multilayer ceramic
capacitor 1 of the present preferred embodiment, the electric field
concentration is reduced or prevented by the first segregation 610,
and thus it is possible to improve the reliability.
[0242] In the multilayer ceramic capacitor 1, the second
segregation 620 by at least one metal element selected from the
group consisting of Mg, Mn, and Si, for example, is present in each
of the end in the width (W) direction of the first internal
electrode layer 21, and the end in the width (W) direction of the
second internal electrode layer 22.
[0243] The electric field is likely to be concentrated at the end
in the width (W) direction of each of the first internal electrode
layer 21 and the second internal electrode layer 22 in contact with
the third dielectric ceramic layers 41 and 42, and when the
electric field concentration occurs, the reliability of a
multilayer ceramic capacitor may be reduced. However, in the
multilayer ceramic capacitor 1 of the present preferred embodiment,
since the electric field concentration is reduced or prevented by
the second segregation 620, it is possible to improve the
reliability.
[0244] In the multilayer ceramic capacitor 1, the first segregation
610 segregated in the first internal electrode layer 21, the first
segregation 610 segregated in the second internal electrode layer
22, the second segregation 620 segregated in the first internal
electrode layer 21, and the second segregation 620 segregated in
the second internal electrode layer 22 are different from one
another in the metal element included in at least one set of
segregations therein.
[0245] As a result, it is possible to provide an optimal metal
element according to the position where the first segregation 610
and the second segregation 620 are provided, and thus it is
possible to improve reliability.
[0246] In the multilayer ceramic capacitor 1 of the present
preferred embodiment, the first dielectric ceramic layer 20a
includes Ba and Ti, and the content of each of the metal element
610a included in the first segregation 610 and the metal element
620a included in the second segregation 620 with respect to the
internal electrode layer is preferably about 0.3 mol % or more, for
example, with respect to 100 moles of Ti.
[0247] Thus, the electric field concentration described above can
be effectively reduced or prevented, and the reliability can be
further improved.
[0248] In the multilayer ceramic capacitor 1 of the present
preferred embodiment, the region where the first segregation 610 is
present in the first internal electrode layer 21 is preferably
about 0.3 .mu.m or more, for example, in the length (L) direction;
the region where the first segregation 610 is present in the second
internal electrode layer 22 is preferably about 0.3 .mu.m or more,
for example, in the length (L) direction; the region where the
second segregation 620 is present in the first segregation 610 is
preferably about 0.3 .mu.m or more, for example, in the width (W)
direction; and the region where the second segregation 620 is
present in the second segregation 620 is preferably about 0.3 .mu.m
or more, for example, in the width (W) direction.
[0249] Thus, the electric field concentration is reduced or
prevented by the segregation, and thus the advantageous effect of
improving the reliability is reliably obtained.
Test Example 3
[0250] Next, Test Example 3 will be described which verifies the
advantageous effects of the first segregation 610 and the second
segregation 620 in the multilayer ceramic capacitor 1 of the
present preferred embodiment.
[0251] As shown in Table 4, Test Examples 3-1 to 3-18 were prepared
for the multilayer ceramic capacitor including the second
dielectric ceramic layer 20b including any one of the elements of
Mg, Mn, Si and the third dielectric ceramic layers 41 and 42. Then,
for each Test Example, the concentration of the element, and the
length in the length (L) direction and the length in the width (W)
direction of the first segregation generated at the end in the
length (L) direction of the first internal electrode layer 21 and
the second internal electrode layer 22 were examined. The
concentrations of the metal elements of the first segregation and
the second segregation were examined by using the same method as
for the concentration of the second alloy portion and the
concentration of the third alloy portion in "Test Example 1"
described above. Furthermore, the length of each of the first
segregation and the second segregation was measured by EDX
analysis.
[0252] For the multilayer ceramic capacitors of Test Examples 3-1
to 3-18, the determination was performed by measuring, after being
cooled to room temperature after being heated for about 1 hour in
an environment with a room temperature of about 150.degree. C., the
resistance value (k.OMEGA.) in a state in which a voltage of about
6.3 V was applied, to examine MTTF (mean failure time). In
addition, whether or not the capacitance was reduced was examined
by an LCR meter (E4980 available from Keysight Technologies). When
the decrease in the capacitance was about 3% or more, or MTTF was
about 15.3 hours or less, it was evaluated as fail, when the
decrease of the capacitance was less than about 3%, and MTTF was
more than about 15.3 hours and less than about 30 hours, it was
evaluated as good, and when the decrease in the capacitance was
less than about 3% and MTTF was more than about 30 hours, it was
evaluated as excellent. The results are listed in Table 4.
TABLE-US-00004 TABLE 4 LENGTH IN LENGTH IN CONCEN- LENGTH WIDTH
TRATION DIRECTION DIRECTION MTTF CAPACITANCE ELEMENT (MOLE %)
(.mu.m) (.mu.m) (hr) DECREASE EVALUATION TEST Si 0.2 0.08 0.07 14.1
0.1% FAIL EXAMPLE DECREASED 3-1 TEST Si 0.3 0.1 0.12 29.7 0.13%
GOOD EXAMPLE DECREASED 3-2 TEST Si 0.5 0.3 0.27 30.8 0.38%
EXCELLENT EXAMPLE DECREASED 3-3 TEST Si 0.55 0.4 0.34 31.5 0.45%
EXCELLENT EXAMPLE DECREASED 3-4 TEST Si 0.6 0.45 0.42 32.3 0.5%
EXCELLENT EXAMPLE DECREASED 3-5 TEST Si 0.7 2.1 3.2 38.9 3.5% FAIL
EXAMPLE DECREASED 3-6 TEST Mg 0.2 0.07 0.05 13.5 0.11% FAIL EXAMPLE
DECREASED 3-7 TEST Mg 0.3 0.1 0.13 29.7 0.13% GOOD EXAMPLE
DECREASED 3-8 TEST Mg 0.5 0.3 0.29 30.8 0.38% EXCELLENT EXAMPLE
DECREASED 3-9 TEST Mg 0.55 0.4 0.42 31.5 0.45% EXCELLENT EXAMPLE
DECREASED 3-10 TEST Mg 0.6 0.45 0.51 32.3 0.5% EXCELLENT EXAMPLE
DECREASED 3-11 TEST Mg 0.7 2.3 3.0 38.9 3.2% FAIL EXAMPLE DECREASED
3-12 TEST Mn 0.2 0.07 0.02 14.9 0.15% FAIL EXAMPLE DECREASED 3-13
TEST Mn 0.3 0.1 0.05 29.7 0.13% GOOD EXAMPLE DECREASED 3-14 TEST Mn
0.5 0.3 0.26 30.8 0.38% EXCELLENT EXAMPLE DECREASED 3-15 TEST Mn
0.55 0.4 0.42 31.5 0.45% EXCELLENT EXAMPLE DECREASED 3-16 TEST Mn
0.6 0.45 0.42 32.3 0.5% EXCELLENT EXAMPLE DECREASED 3-17 TEST Mn
0.7 1.9 2.5 33.5 3.2% FAIL EXAMPLE DECREASED 3-18
[0253] By allowing the second dielectric layer to include Mg, Mn,
and Si, so as to produce a segregated portion at the end in the
length direction and the width direction of the internal electrode,
it is possible to eliminate the reliability degradation factor
which is likely to occur at the end thereof. However, if the
content is too large, the region which defines and functions as a
metal of the internal electrode becomes narrow, resulting in a
decrease in capacitance.
(6) Segregation Formed in the Corner Region of the Internal
Electrode Layer Side of the Second Dielectric Ceramic Layer
[0254] When the first segregation 610 and the second segregation
620 described above are included, a third segregation 630 is
preferably present as shown in FIG. 33. The third segregation 630
is present in each of a first corner region 710 and a second corner
region 720.
[0255] The first corner region 710 is a region in which the length
(L) direction in which the first segregation 610 exists overlaps
the width (W) direction in which the second segregation 620 exists,
in the first internal electrode layer 21. Furthermore, the second
corner region 720 is a region in which the length (L) direction in
which the first segregation 610 exists overlaps the width (W)
direction in which the second segregation 620 exists, in the second
internal electrode layer 22. The third segregation 630 is generated
by the segregation of the metal element 610a of the first
segregation 610 and the metal element 620a of the second
segregation 620.
[0256] In a preferred embodiment of the present invention, it is
preferable for the metal element 610a included in the first
segregation 610 and the metal element 620a included in the second
segregation 620 to be different from each other, and the metal
element 630a of the third segregation 630 include both the metal
element 610a included in the first segregation 610 and the metal
element 620a included in the second segregation 620.
[0257] Furthermore, in a preferred embodiment of the present
invention, the region where the first segregation 610 exists is
preferably about 0.1 .mu.m or more, for example, in the length (L)
direction, and the region where the second segregation 620 exists
is preferably about 0.1 .mu.m or more, for example, in the width
(W) direction.
[0258] FIG. 33 shows a plane including the length (L) direction and
the width (W) direction in the multilayer ceramic capacitor 1. The
third segregation 630 is preferably segregated in a substantially
right-angled triangular shape so that the region where the third
segregation 630 exists becomes larger as approaching the end in the
length (L) direction in the plane including the length (L)
direction and the width (W) direction. A portion or all of the
third segregation 630 is included in the near intersection region
440 in FIG. 19.
[0259] Furthermore, in the multilayer ceramic capacitor 1, it is
preferable for the second dielectric ceramic layer 20b to be
arranged with respect to the first internal electrode layer 21 and
the second internal electrode layer 22 so that a portion thereof is
superimposed on the region where the third segregation 630 exists
in the stacking (T) direction. More specifically, for example, as
shown in FIG. 34, the end of the second dielectric ceramic layer
20b is superimposed, in the length (L) direction, on the end of the
second internal electrode layer 22 in the region including the
third segregation 630. Similarly to this, the end of the second
dielectric ceramic layer 20b may be superimposed on the end of the
first internal electrode layer 21. In such a mode in which the end
in the length (L) direction is superimposed thereon, the end of the
first internal electrode layer 21 or the end of the second
dielectric ceramic layer 20b may be superimposed on the end of the
second dielectric ceramic layer 20b.
[0260] In the multilayer ceramic capacitor 1, the first segregation
610 by at least one metal element selected from the group
consisting of Mg, Mn, and Si is present in each of the end of the
first internal electrode layer 21 in the length (L) direction which
is not connected to the second external electrode 52, and the end
of the second internal electrode layer 22 in the length (L)
direction which is not connected to the first external electrode
51; the second segregation 620 by at least one metal element
selected from the group consisting of Mg, Mn, and Si is present in
each of the end of the first internal electrode layer 21 in the
width (W) direction, and the end of the second internal electrode
layer 22 in the width (W) direction; and the third segregation 630
by the respective metal elements of the first segregation 610 and
second segregation 620 is present in each of the first corner
region 710 where the end in the length (L) direction in which the
first segregation 610 exists in the first internal electrode layer
21 overlaps the width (W) direction in which the second segregation
620 exists in the first internal electrode layer 21, and the second
corner region 720 where the end in the length (L) direction in
which the first segregation 610 exists in the second internal
electrode layer 22 overlaps the width (W) direction in which the
second segregation 620 exists.
[0261] The electric field is likely to be concentrated at the first
corner region 710 and the second corner region 720, and when the
electric field concentration occurs, the reliability of a
multilayer ceramic capacitor may be degraded. However, in the
multilayer ceramic capacitor 1 of the present preferred embodiment,
since the electric field concentration to the first corner region
710 and the second corner region 720 is reduced or prevented by the
third segregation 630, the reliability can be improved.
[0262] In the multilayer ceramic capacitor 1 of the present
preferred embodiment, the metal element 610a included in the first
segregation 610 and the metal element 620a included in the second
segregation 620 are different from each other, and the metal
element included in the third segregation 630 includes both the
metal element 610a included in the first segregation 610 and the
metal element 620a included in the second segregation 620.
[0263] As a result, it is possible for the third segregation 630 to
reduce or prevent the electric field concentration to the first
corner region 710 and the second corner region 720, thus improving
the reliability.
[0264] It should be noted that, in the third segregation 630, Mg is
preferably used as the metal element disposed on the side close to
the third dielectric ceramic layers 41 and 42. On the other hand,
in the third segregation 630, Si is preferably used as the metal
element disposed on the side close to the second dielectric ceramic
layer 20b, from the viewpoint of the possibility of improving
moisture resistance. Therefore, it is preferable for both Mg and Si
to be segregated in the first corner region 710 and the second
corner region 720. In addition, there is a possibility that the
short-circuit recovery is performed due to the first segregation
610 at the ends in the width (W) direction of the first internal
electrode layer 21 and the second internal electrode layer 22.
Furthermore, it is more preferable for Sn to be a solid solution in
the first internal electrode layer 21 and the second internal
electrode layer 22.
[0265] In the multilayer ceramic capacitor 1 of the present
preferred embodiment, preferably, the region where the first
segregation 610 exists is about 0.1 .mu.m or more in the length (L)
direction, and the region where the second segregation 620 exists
is about 0.1 .mu.m or more in the width (W) direction, for example.
Thus, the electric field concentration is reduced or prevented by
segregation, and the advantageous effect of improving the
reliability is reliably obtained.
[0266] In the multilayer ceramic capacitor 1 of the present
preferred embodiment, the region where the third segregation 630
exists becomes larger approaching the end in the length (L)
direction in a plane including the length (L) direction and the
width (W) direction.
[0267] Thus, the area of the third segregation 630 in the portion
of the end of the second dielectric ceramic layer 20b in the length
(L) direction where the electric field concentration is likely to
occur increases, and reduction or prevention of the electric field
concentration by the third segregation 630 is achieved more
effectively, thus making it possible to further improve the
reliability.
[0268] In the multilayer ceramic capacitor 1 of the present
preferred embodiment, the second dielectric ceramic layer 20b is
arranged with respect to the first internal electrode layer 21 and
the second internal electrode layer 22 so that a portion thereof is
superimposed on the region where the third segregation 630 exists
in the stacking (T) direction.
[0269] Thus, the region where the third segregation 630 exists is
likely to become larger approaching the end in the length (L)
direction in the plane including the length (L) direction and the
width (W) direction.
Test Example 4
[0270] Next, Test Example 4 will be described which verifies the
advantageous effects of the third segregation 630 in the multilayer
ceramic capacitor 1.
[0271] As shown in Table 5, Test Examples 4-1 to 4-18 were prepared
for the multilayer ceramic capacitors each including the second
dielectric ceramic layer including any one of the metal elements of
Mg, Mn, and Si, and the third dielectric ceramic layer including
any one of Mg, Mn, and Si. Then, the concentration of the metal
element included in the third segregation occurring in the first
corner region and the second corner region of each of the
multilayer ceramic capacitor, the length of the length (L)
direction and the length of the width (W) direction were examined.
The concentration of the metal element of the third segregation was
examined by using the same method as the concentration of the
second alloy portion and the concentration of the third alloy
portion in "Test Example 1" described above. Also, the respective
lengths of the third segregation were measured by EDX analysis.
[0272] For the multilayer ceramic capacitors of Test Examples 4-1
to 4-14, the determination was performed by measuring the
resistance value (k.OMEGA.) in a state in which a voltage of about
6.3 V was applied in an environment with a room temperature of
about 150.degree. C., to examine MTTF (mean failure time). MTTF was
determined when the resistance value became about 10 k.OMEGA. or
less, and if MTTF was about 15.3 hours (hr) or less, it was
evaluated as fail, if MTTF was up to about 30 hours beyond about
15.3 hours (hr), it is evaluated as good, and if MTTF was beyond
about 30 hours, it was evaluated as excellent. The results are
listed in Table 5. In addition, whether or not the capacitance was
reduced was examined by an LCR meter (E4980 available from Keysight
Technologies), and those showing the reduction of capacitance of
about 3% or more were evaluated as fail. It should be noted that,
when the coverage of the internal electrode layer is less than
about 80%, since the capacitance is difficult to be measured, it
was evaluated as unmeasurable.
TABLE-US-00005 TABLE 5 SEGREGATION SEGREGATION LENGTH IN CONCEN-
LENGTH IN LENGTH TRATION WIDTH DIRECTION MTTF ELEMENT (MOLE %)
DIRECTION (.mu.m) (hr) EVALUATION TEST Si 0.2 0.07 0.05 15.2 FAIL
EXAMPLE 4-1 TEST Si 0.3 0.1 0.1 27.3 GOOD EXAMPLE 4-2 TEST Si 0.5
1.1 1.1 32.1 EXCELLENT EXAMPLE 4-3 TEST Si 0.55 1.3 1.3 33.4
EXCELLENT EXAMPLE 4-4 TEST Si 0.6 1.5 1.5 35.6 EXCELLENT EXAMPLE
4-5 TEST Si 0.7 2.12 2.12 38.9 FAIL EXAMPLE 4-6 CAPACITANCE
DECREASED 3% TEST Mg 0.2 0.08 0.07 14.8 FAIL EXAMPLE 4-7 TEST Mg
0.3 0.1 0.1 27.3 GOOD EXAMPLE 4-8 TEST Mg 0.5 1.1 1.1 32.1
EXCELLENT EXAMPLE 4-9 TEST Mg 0.55 1.3 1.3 33.4 EXCELLENT EXAMPLE
4-10 TEST Mg 0.6 1.5 1.5 35.6 EXCELLENT EXAMPLE 4-11 TEST Mg 0.7
2.11 2.11 38.9 FAIL EXAMPLE 4-12 CAPACITANCE DECREASED 3% TEST Mn
0.2 0.06 0.07 13.5 FAIL EXAMPLE 4-13 TEST Mn 0.3 0.1 0.1 27.3 GOOD
EXAMPLE 4-14 TEST Mn 0.5 1.1 1.1 32.1 EXCELLENT EXAMPLE 4-15 TEST
Mn 0.55 1.3 1.3 33.4 EXCELLENT EXAMPLE 4-16 TEST Mn 0.6 1.5 1.5
35.6 EXCELLENT EXAMPLE 4-17 TEST Mn 0.7 1.7 1.6 42.5 FAIL EXAMPLE
4-18 CAPACITANCE DECREASED 3%
[0273] By allowing the second ceramic dielectric layer and the
third ceramic dielectric layer to include Si, Mg, and Mn, it is
possible to produce many segregation regions in the corners. In
particular, electric field concentration occurs in the corner,
which tends to degrade the reliability. However, it is possible to
improve the reliability by producing a segregated region. However,
if the content is too large, the region which functions as a metal
of the internal electrode becomes narrow, resulting in a reduction
in capacitance.
(7) Thickness of the Second Dielectric Ceramic Layer
[0274] FIG. 35 schematically shows the WT cross-section at the
central portion in the length (L) direction of the multilayer body
10 in the multilayer ceramic capacitor 1, and respectively shows,
in this cross-section, the thickness of the first dielectric
ceramic layer 20a as T1 and the thickness at the end in the width
(W) direction as T2.
[0275] Furthermore, FIG. 36 shows a portion of the LT cross-section
of the multilayer ceramic capacitor 1 of the present preferred
embodiment, and T3 refers to the thickness of the second dielectric
ceramic layer 20b. Although FIG. 36 shows the second dielectric
ceramic layer 20b in contact with the second internal electrode
layer 22, the thickness of the second dielectric ceramic layer 20b
in contact with the first internal electrode layer 21 is also
regarded as T3. In other words, the thickness T3 of the second
dielectric ceramic layer 20b refers to each of the thicknesses
between the end of the first internal electrode layer 21 in the
length (L) direction which is not connected to the second external
electrode 52, and the second external electrode 52, and between the
end of the second internal electrode layer 22 in the length (L)
direction which is not connected to the first external electrode 51
and the second external electrode 52.
[0276] In a preferred embodiment of the present invention, the
difference in thickness between T1 and T2 is relatively small and
is within about 10% of T1. In contrast, the thickness of T3 is
larger than T1 and T2, and the difference is preferably, for
example, about 10% or more of T1 and T2.
[0277] The method of increasing the thickness T3 of the second
dielectric ceramic layer 20b more than the thicknesses T1 and T2 of
the first dielectric ceramic layer 20a is not limited to the method
described above and, for example, a method is also possible by
causing the end of the unfired second dielectric ceramic layer 120b
in the length (L) direction to be superimposed on the ends of the
unfired first internal electrode layer 121 and the unfired second
internal electrode layer 122 in the length (L) direction, when
fabricating the green chip 110 before firing, following which the
green chip 110 is fired.
[0278] Among T1, T2, and T3, the thickness T1 of the central
portion of the first dielectric ceramic layer 20a is preferably
about 0.7 .mu.m or less, for example. The thickness T3 of the
second dielectric ceramic layer 20b is preferably about 0.4 .mu.m
or more, for example.
[0279] In the multilayer ceramic capacitor 1, in a plane including
the center portion in the length (L) direction, and the stacking
(T) direction and the width (W) direction of the first dielectric
ceramic layer 20a, when the thickness at the center portion in the
stacking (T) direction is defined as T1, the thickness at the end
of the first dielectric ceramic layer 20a in the width (W)
direction is defined as T2, and the respective thicknesses between
the end of the first internal electrode layer 21 in the length (L)
direction which is not connected to the second external electrode
52, and the second external electrode 52 and between the end of the
second internal electrode layer 22 in the length (L) direction
which is not connected to the first external electrode 51, and the
first external electrode 51 is defined as T3, the difference in
thickness between T1 and T2 is within 10% of T1, the thickness of
T3 is greater than T1 and T2, and the difference thereof is
preferably, for example, about 10% or more of T1 and T2.
[0280] Thus, the element thickness by the second dielectric ceramic
layer 20b disposed for the purpose of level difference elimination
is provided sufficiently between the first dielectric ceramic layer
20a sandwiching the first internal electrode layer 21 and the
second internal electrode layer 22, a result of which it is
possible to improve the reliability.
[0281] While preferred embodiments of the present invention have
been described above, it is to be understood that variations and
modifications will be apparent to those skilled in the art without
departing from the scope and spirit of the present invention. The
scope of the present invention, therefore, is to be determined
solely by the following claims.
* * * * *